US6864392B2 - α-Sulfin and α-Sulfonamino amide derivatives - Google Patents

α-Sulfin and α-Sulfonamino amide derivatives Download PDF

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US6864392B2
US6864392B2 US10/257,085 US25708503A US6864392B2 US 6864392 B2 US6864392 B2 US 6864392B2 US 25708503 A US25708503 A US 25708503A US 6864392 B2 US6864392 B2 US 6864392B2
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formula
alkyl
compound
optionally substituted
hydrogen
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US20040092401A1 (en
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Martin Zeller
Clemens Lamberth
Henry Szczepanski
Alain De Mesmaeker
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Syngenta Crop Protection LLC
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/06—Sulfonic acid amides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C307/00—Amides of sulfuric acids, i.e. compounds having singly-bound oxygen atoms of sulfate groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C307/04—Diamides of sulfuric acids
    • C07C307/06—Diamides of sulfuric acids having nitrogen atoms of the sulfamide groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
    • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C311/03—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C311/06—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms to acyclic carbon atoms of hydrocarbon radicals substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C313/02—Sulfinic acids; Derivatives thereof
    • C07C313/06—Sulfinamides

Definitions

  • the present invention relates to novel ⁇ -sulfin and ⁇ -sulfonamino acid amides of formula I below. It relates to the preparation of those substances and to agrochemical compositions comprising at least one of those compounds as active ingredient. The invention relates also to the preparation of the said compositions and to the use of the compounds or of the compositions in controlling or preventing the infestation of plants by phytopathogenic microorganisms, especially fungi.
  • the invention relates to ⁇ -sulfin- and ⁇ -sulfonamino acid amides of the general formula I including the optical isomers thereof and mixtures of such isomers, wherein
  • aryl includes aromatic hydrocarbon rings like phenyl, naphthyl, anthracenyl, phenanthrenyl, with phenyl being preferred.
  • Heteroaryl stands for aromatic ring systems comprising mono-, bi- or tricyclic systems wherein at least one oxygen, nitrogen or sulfur atom is present as a ring member.
  • Examples are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalin
  • aryl and heteroaryl groups may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time.
  • substituents of aryl or heteroaryl groups are: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl and phenyl-alkyl, it being possible in turn for all of the preceding groups to carry one or more identical or different halogen atoms; alkoxy; alkenyloxy; alkynyloxy; alkoxyalkyl; halogenalkoxy, alkylthio; halogenalkylthio; alkyl sulfonyl; formyl; alkanoyl; hydroxy; halogen; cyano; nitro; amino; alkylamino; dialkyl amino; carboxy; alkoxycarbonyl; alkenyloxycarbonyl; alkynyloxycarbonyl.
  • halogen or the prefix “halo” includes fluorine, chlorine, bromine and iodine.
  • alkyl, alkenyl and alkynyl radicals may be straight-chain or branched. This applies also to the alkyl, alkenyl or alkynyl parts of other alkyl-, alkenyl- or alkynyl-containing groups.
  • alkyl on its own or as part of another substituent is to be understood as being, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the isomers thereof, for example isopropyl, isobutyl, tert-butyl or sec-butyl, isopentyl or tert-pentyl.
  • Cycloalkyl is, depending upon the number of carbon atoms mentioned, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • alkenyl as a group or as a structural element of other groups is to be understood as being, for example, ethenyl, allyl, 1-propenyl, buten-2-yl, buten-3-yl, penten-1-yl, penten-3-yl, hexen-1-yl, 4-methyl-3-pentenyl or 4-methyl-3-hexenyl.
  • Alkynyl as a group or as a structural element of other groups is, for example, ethynyl, propyn-1-yl, propyn-2-yl, butyn-1-yl, butyn-2-yl, 1-methyl-2-butynyl, hexyn-1-yl, 1-ethyl-2-butynyl or octyn-1-yl.
  • a halogenalkyl group may contain one or more (identical or different) halogen atoms, and for example may stand for CHCl 2 , CH 2 F, CCl 3 , CH 2 Cl, CHF 2 , CF 3 , CH 2 CH 2 Br, C 2 Cl 5 , CH 2 Br, CHClBr, CF 3 CH 2 , etc.
  • R 2 and R 3 together with the carbon atom to which they are attached form a hydrocarbon ring the ring corresponds to cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane or cyclooctane.
  • R 9 and R 10 together with the nitrogen atom to which they are attached form a ring system the ring corresponds to pyrrolidine or piperidine.
  • the presence of at least one asymmetric carbon atom and/or at least one asymmetric oxidized sulfur atom in the compounds of formula I means that the compounds may occur in optically isomeric forms. As a result of the presence of a possible aliphatic C ⁇ C double bond, geometric isomerism may also occur.
  • Formula I is intended to include all those possible isomeric forms and mixtures thereof.
  • Preferred individual compounds are:
  • ⁇ -sulfin- and ⁇ -sulfonamino acid derivatives having a different kind of molecular structure have already been proposed for controlling plant-destructive fungi (for example in WO 95/030651, WO 97/14677, WO 98/38160, WO 98/38161 and WO 99/07674).
  • ⁇ -sulfin- and ⁇ -sulfonamino acid amides of formula I may be obtained according to one of the following processes: a)
  • Carboxy-activated derivatives of the amino acid of formula II encompasses all compounds having an activated carboxyl group like an acid halide, such as an acid chloride, like symmetrical or mixed anhydrides, such as mixed anhydrides with O-alkylcarbonates, like activated esters, such as p-nitrophenylesters or N-hydroxysuccinimidesters, as well as in situ produced activated forms of the amino acid of formula II by condensating agents, such as dicyclohexylcarbodiimide, carbonyldiimidazol, benzotriazol-1-yloxy-tris (dimethylamino)phosphonium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-bis(penta methylene)uronium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-bis(tetramethylene)uronium hex
  • the mixed anhydrides of the amino acids of the formula II may be prepared by reaction of an amino acid of formula II with chloroformic acid esters like chloroformic acid alkylesters, such as ethyl chloroformate or isobutyl chloroformate, optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine.
  • chloroformic acid esters like chloroformic acid alkylesters, such as ethyl chloroformate or isobutyl chloroformate
  • an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine.
  • the present reaction is preferably performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; amides, e.g. N,N-dimethylformamide; nitriles e.g. acetonitrile; or ethers e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is also possible to use mixtures of these solvents.
  • aromatic, non-aromatic or halogenated hydrocarbons such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; amides, e
  • the reaction is preformed optionally in the presence of an organic or inorganic base like a tertiary amine, e.g. triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from ⁇ 80° C. to +150° C., preferentially at temperatures ranging from ⁇ 40° C. to +40° C.
  • an organic or inorganic base like a tertiary amine, e.g. triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an al
  • the compounds of formula II may be prepared by reaction of an amino acid of formula IV where R 2 and R 3 are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V where R 1 and n have the same meanings as defined above and where X is halide, preferentially chlorine or bromine (step A).
  • the reaction may be performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons, e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is also possible to use mixtures of these solvents.
  • aromatic, non-aromatic or halogenated hydrocarbons such as chlorohydrocarbons, e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or
  • the reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from ⁇ 80° C. to +150° C., preferentially at temperatures ranging from ⁇ 40° C. to +40° C. b)
  • a tertiary amine such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine
  • an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-
  • the compounds of formula I may also be prepared by reaction of an amino acid derivative of formula VI wherein R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V wherein R 1 and n are as defined for formula I and X is halide, preferentially chlorine or bromine (step C).
  • step C preferentially chlorine or bromine
  • the compounds of formula I may also be prepared by reaction of a phenol of formula VII wherein R 1 , n, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined for formula I with a compound of formula VIII wherein R 8 is as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate (step D).
  • the reaction may be performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones e.g.
  • esters e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane, amides, e.g. dimethylformamide, nitriles, e.g. acetonitrile, alcohols, e.g. methanol, ethanol, isopropanol, n-butanol or tert-butanol, sulfoxides e.g. dimethylsulfoxide or water. It is also possible to use mixtures of these solvents.
  • the reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide, a metal carbonate or a metal alkoxide, preferentially an alkali hydroxide, an alkali carbonate or an alkali alkoxide, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide or potassium tert-butoxide at temperatures ranging from ⁇ 80° C. to +200° C., preferentially at temperatures ranging from 0° C. to +120° C. d)
  • an organic or inorganic base like a tertiary amine, such as
  • the compounds of formula Ia may also be prepared via formula IX wherein R 1 , n, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 11 , R 12 and R 13 are defined for formula I by reacting of a phenol of formula VII wherein R 1 , n, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined for formula I with a compound of formula VIIIa wherein R 11 , R 12 and R 13 are as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate (step E).
  • a halide such as a chloride or bromide
  • a sulfonic ester such as a tosylate, mesylate or triflate
  • reaction is performed in the same manner as described for step D.
  • the compounds of formula Ia R 11 , R 12 and R 13 is as defined for formula I may be prepared by reaction of compounds of formula IX with hydrogen.
  • the reaction is performed in a solvent like ethers, e.g. diethylether, dioxane or tetrahydrofuran, or like alcohols, e.g. methanol or ethanol, or water in the presence of transition metals or transition metal salts, e.g. nickel, cobalt, palladium, platinum or rhodium, optionally in the presence of bases, e.g. ammonia, or in the presence of salts, e.g. barium sulfate, at temperatures ranging from ⁇ 20° C. to +160° C. and at pressures ranging from 1 to 200 bar.
  • the intermediate amines of formula III may be obtained by one of the following processes:
  • Step 1 is the alkylation of a phenol with a compound of formula VIII.
  • the reaction is performed in the same manner as described for procedure c).
  • Step 2 is the reaction of an aromatic aldehyde with nitromethane. This reaction is performed in a solvent like an organic carboxylic acids, e.g. acetic acid optionally in the presence of the ammonium salt of this carboxylic acid, e.g. ammonium acetate at temperatures ranging from 0° C. to +200° C.
  • a solvent like an organic carboxylic acids e.g. acetic acid optionally in the presence of the ammonium salt of this carboxylic acid, e.g. ammonium acetate at temperatures ranging from 0° C. to +200° C.
  • Step 3 is the reduction of an unsaturated nitrogen-compound.
  • This reaction is performed in a solvent like an ether, e.g. diethylether, dioxane or tetrahydrofuran, or an alcohol, e.g. methanol, ethanol or isopropanol, with borohydride, with a boron-complex, e.g. the complex of borohydride with tetrahyrofuran, with an alkaliborohydride, with an alkalialuminiumhydride, e.g.
  • a transition metal e.g. nickel, cobalt, palladium, platinium or rhodium at temperatures ranging from ⁇ 50° C. to +200° C.
  • Step 4 is the reaction of an aldehyde or a ketone of formula XXIII with hydroxylamine or with a salt of hydroxylamine.
  • This reaction is performed in a solvent like an alcohol, e.g. methanol, ethanol or isopropanol, like an ether, e.g. diethylether, dioxane or tetrahydrofuran, like an amide, e.g. dimethylformamide, or in water or in a mixture of these solvents optionally in the presence of an organic or inorganic base like a tertiary amine, e.g. triethylamine, like a heterocyclic compound containing nitrogen, e.g. pyridine, or like an alkalicarbonate, e.g. sodium carbonate or potassium carbonate, at temperatures ranging from ⁇ 20° C. to +150° C.
  • an alcohol e.g. methanol, ethanol or isopropanol
  • an ether
  • Step 5 is the exchange of hydroxy by cyanide.
  • This reaction is performed in an organic solvent like an amide, e.g. dimethylformamide using a metal cyanide like an alkali cyanide, e.g. sodium cyanide or potassium cyanide, at temperatures ranging from 0° C. to +200° C.
  • a metal cyanide like an alkali cyanide, e.g. sodium cyanide or potassium cyanide
  • Step 6 is the hydrolysis of an alkyl ester.
  • This reaction is performed in a solvent like an alcohol, e.g. methanol, ethanol or isopropanol, like an ether, e.g. diethylether, dioxane or tetrahydrofuran, like a halogenated hydrocarbon, e.g. dichloromethane, or water or in a mixture of these solvents optionally in the presence of an alkali hydroxide, e.g. lithium hydroxide, sodium hydroxide or potassium hydroxide, or optionally in the presence of an acid, e.g. hydrogen chloride, sulfuric acid or trifluoroacetic acid at temperatures ranging from ⁇ 20° C. to +160° C.
  • an alcohol e.g. methanol, ethanol or isopropanol
  • an ether e.g. diethylether, dioxane or tetrahydrofuran
  • a halogenated hydrocarbon
  • Step 7 is the reaction of a carboxylic acid or the activated form of this carboxylic acid with hydrogen azide or an azide-salt.
  • An activated form of a carboxylic acid can be the acid halogenide, e.g. acid chloride, a symmetric or a mixed anhydride.
  • Azide-salts can be alkali azides, e.g. sodium azide.
  • the reaction is performed in a solvent like a hydrocarbon, e.g. toluene or xylene, like a halogenated hydrocarbon, e.g. chloroform, like an ether, e.g. dioxane, like a ketone, e.g.
  • acetone or 2-butanone like an alcohol, e.g. methanol, ethanol or tert-butanol, or water or in a mixture of these solvents optionally in the presence of an acid like an inorganic acid, e.g. sulfuric acid or hydrogen chloride at temperatures ranging from ⁇ 40° C. to +200° C.
  • an acid like an inorganic acid, e.g. sulfuric acid or hydrogen chloride at temperatures ranging from ⁇ 40° C. to +200° C.
  • the compounds of formula XXVI are prepared starting from compounds of the formula XXV by applying step 5 and step 1 in the same pot.
  • Amines of formula VI can be obtained by the following process: wherein R is lower alkyl or optionally substituted benzyl.
  • Step 8 is the amidation of an carbamate-protected amino acid of formula XXXIII with an amine of formula XXXIV.
  • the reaction is performed in the same manner as described for step A.
  • Step 9 is the alkylation of a phenol of formula XXXV with an compound of formula VIII.
  • the reaction is performed in the same manner as described for step D.
  • Step 10 is the hydrolysis of a carbamate of formula XXXVI.
  • the reaction is performed in a solvent like hydrocarbons, e.g. toluene, like halogenated hydrocarbons, e.g. dichloromethane, like ketones, e.g. acetone, like esters, e.g. ethyl acetate, like ethers, e.g. dioxane or tetrahydrofuran, or like water or in mixtures of these solvents optionally in the presence of an organic acid like carboxylic acid, e.g. trifluoroacetic acid, or like a sulfonic acid, e.g. methanesulfonic acid or toluenesulfonic acid, or in the presence of an inorganic acid, e.g. hydrogen chloride or sulfuric acid, at temperatures ranging from ⁇ 40° C. to +160° C.
  • an organic acid e.g. hydrogen chloride or sulfuric
  • the compounds of formula I are oils or solids at room temperature and are distinguished by valuable microbiocidal properties. They can be used in the agricultural sector or related technical fields preventively and curatively for the control of plant-destructive microorganisms.
  • the compounds of formula I according to the invention are distinguished at low rates of concentration not only by outstanding microbiocidal, especially fungicida I, activity but also by being especially well tolerated by the treated crop plants.
  • the compounds of formula I have a very advantageous biocidal spectrum in the control of phytopathogenic microorganisms, especially fungi.
  • the compounds of formula I it is possible to inhibit or destroy phytopathogenic microorganisms that occur on various crops of useful plants or on parts of such plants (fruit, blossom, leaves, stems, tubers, roots), while parts of the plants which grow later also remain protected, for example, against phyto pathogenic fungi.
  • novel compounds of formula I prove to be effective against specific genera of the fungus classes Fungi imperfecti (e.g. Cercospora ), Basidio mycetes (e.g. Puccinia ) and Ascomycetes (e.g. Erysiphe and Venturia ) and especially against Oomycetes (e.g. Plasmopara, Peronospora, Pythium and Phytophthora ). They therefore represent in plant protection a valuable addition to the compositions for controlling phyto pathogenic fungi.
  • the compounds of formula I can also be used as coatings or dressings for protecting seed (fruit, tubers, grains) and plant cuttings from fungal infections and against phyto pathogenic fungi that occur in the soil.
  • the invention relates also to compositions comprising compounds of formula I as active ingredient, especially plant-protecting compositions, and to the use thereof in the agricultural sector or related fields.
  • the present invention includes the preparation of those compositions, wherein the active ingredient is homogeneously mixed with one or more of the substances or groups of substances described herein. Also included is a method of treating plants which is distinguished by the application of the novel compounds of formula I or of the novel compositions.
  • Target crops to be protected within the scope of this invention comprise, for example, the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucurbitaceae (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamon, camphor) and plants such as
  • the compounds of formula I are normally used in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with other active ingredients.
  • Those other active ingredients may be fertilisers, micronutrient donors or other preparations that influence plant growth. It is also possible to use selective herbicides or insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of those preparations, if desired together with further carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology.
  • the compounds of formula I can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities.
  • azoles such as azoles, such as azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinyl carbinols, such as ancymidol, fenarimol, nuarimol; 2-amino-pyrimidines, such as bupirimate, di
  • Suitable carriers and surfactants may be solid or liquid and correspond to the substances ordinarily employed in formulation technology, such as e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers. Such carriers and additives are described, for example, in WO 95/30651.
  • a preferred method of applying a compound of formula I, or an agrochemical composition comprising at least one of those compounds, is application to the foliage (foliar application), the frequency and the rate of application depending upon the risk of infestation by the pathogen in question.
  • the compounds of formula I may also be applied to seed grains (coating) either by impregnating the grains with a liquid formulation of the active ingredient or by coating them with a solid formulation.
  • the compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and are for that purpose advantageously formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and by encapsulation in e.g. polymer substances.
  • the methods of application such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • Advantageous rates of application are normally from 1 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, especially from 25 g to 750 g a.i./ha.
  • rates of from 0.001 g to 1.0 g of active ingredient per kg of seed are advantageously used.
  • compositions, preparations or mixtures comprising the compound(s) (active ingredient(s)) of formula I and, where appropriate, a solid or liquid adjuvant are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
  • extenders e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
  • the agrochemical compositions usually comprise 0.01 to 99% by weight, preferably 0.1 to 95% by weight, of a compound of formula I, 99.99 to 1% by weight, preferably 99.9 to 5% by weight, of a solid or liquid adjuvant, and 0 to 25% by weight, preferably 0.1 to 25% by weight, of a surfactant.
  • compositions may also comprise further ingredients, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.
  • further ingredients such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.
  • R 1 R 3 R 8 001 CH 3 — CH 3 —CH 2 — CH 3 —(CH 2 ) 3 —C ⁇ C—CH 2 — 002 CH 3 —CH 2 — CH 3 —CH 2 — CH 3 —(CH 2 ) 3 —C ⁇ C—CH 2 — 003 (CH 3 ) 2 N— CH 3 —CH 2 — CH 3 —(CH 2 ) 3 —C ⁇ C—CH 2 — 004 CH 3 —CH 2 —CH 2 — CH 3 —CH 2 — CH 3 —(CH 2 ) 3 —C ⁇ C—CH 2 — 005 (CH 3 ) 2 CH— CH 3 —CH 2 — CH 3 —(CH 2 ) 3 —C ⁇ C—CH 2 — 006 Cl—CH 2 —CH 2 —CH 2 — CH 3 —CH 2 — CH 3 —(CH 2 ) 3 —C ⁇ C—CH 2 — 007 CH 3
  • R 1 R 3 001 (CH 3 —CH 2 ) 2 N— CH 3 —CH 2 — 002 CH 3 —CH 2 —(CH 3 )N— CH 3 —CH 2 — 003 CH 3 —CH 2 — 004 CH 3 —(CH 2 ) 2 —CH 2 — CH 3 —CH 2 — 005 (CH 3 ) 2 CH—CH 2 — CH 3 —CH 2 — 006 CH 3 —CH 2 —(CH 3 )CH— CH 3 —CH 2 — 007 (CH 3 ) 3 C— CH 3 —CH 2 — 008 CH 2 ⁇ CH— CH 3 —CH 2 — 009 CH 3 —CH 2 — 010 (CH 3 —CH 2 ) 2 N— (CH 3 ) 2 CH— 011 CH 3 —CH 2 —(CH 3 )N— (CH 3 ) 2 CH— 012 (CH 3 ) 2 CH— 013 CH 3 —(
  • Formulations may be prepared analogously to those described in, for example, WO 95/30651.
  • Compounds of Tables 1 to 15 exhibit a good fungicidal action against Plasmopara viticola on vines.
  • Compounds A1.1, A1.2, A1.3, A1.4, A1.5 and A1.6 at 200 ppm inhibit fungal infestation in this test to a least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.

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Abstract

The invention relates to novel pesticidally active α-sulfin- and α-sulfonamino acid amides of the general formula (I) including the optical isomers thereof and mixtures of such isomers, wherein n is a number zero or one, R1-R7 have the meanings given in the specification. R8 is either hydrogen, (a), (b), (c), (d) or (e) wherein R11, R12, R14, R15 and R17 are each independently hydrogen or C1-C4alkyl, R13 is C4-C12alkyl; C1-C12 halogenalkyl; C3-C8 cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl, R16 is optionally substituted aryl or optionally substituted heteroaryl; and Z is oxygen, sulfur —CR18R19— or —NR20—, wherein R18, R19, R20 independently of each other are hydrogen or C1-C4alkyl. The novel compounds possess plant-protecting properties and are suitable for protecting plants against infestation by phytopathogenic microorganisms
Figure US06864392-20050308-C00001

Description

This application is a 371 of PCT/EP01/04207, filed Apr. 11, 2001.
The present invention relates to novel α-sulfin and α-sulfonamino acid amides of formula I below. It relates to the preparation of those substances and to agrochemical compositions comprising at least one of those compounds as active ingredient. The invention relates also to the preparation of the said compositions and to the use of the compounds or of the compositions in controlling or preventing the infestation of plants by phytopathogenic microorganisms, especially fungi.
The invention relates to α-sulfin- and α-sulfonamino acid amides of the general formula I
Figure US06864392-20050308-C00002
including the optical isomers thereof and mixtures of such isomers,
wherein
    • n is a number zero or one;
    • R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfonyl, C3-C8cycloalkyl, cyano, C1-C6alkoxycarbonyl, C3-C8alkenyloxycarbonyl or C3-C6alkynyloxycarbonyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12halogenalkyl; or a group NR9R10 wherein R9 and R10 are each independently of the other hydrogen or C1-C6alkyl, or together are tetra- or penta-methylene;
    • R2 and R3 are each independently hydrogen; C1-C8alkyl; C1-C8alkyl substituted with hydroxy, mercapto, C1-C4alkoxy or C1-C4alkylthio: C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl; C3-C8cycloalkyl-C1-C4alkyl; or the two groups R2 and R3 together with the carbon atom to which they are bonded form a three- to eight-membered hydrocarbon ring;
    • R4, R5, R6 and R7 are each independently hydrogen or C1-C4alkyl;
      Figure US06864392-20050308-C00003
    • R11, R12, R14, R15 and R17 are each independently hydrogen or C1-C4alkyl,
    • R13 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl,
    • R16 is optionally substituted aryl or optionally substituted heteroaryl, and
    • Z is oxygen, sulfur —CR18R19— or —NR20—, wherein R18, R19 and R20 independently of each other are hydrogen or C1-C4alkyl.
In the above definition aryl includes aromatic hydrocarbon rings like phenyl, naphthyl, anthracenyl, phenanthrenyl, with phenyl being preferred.
Heteroaryl stands for aromatic ring systems comprising mono-, bi- or tricyclic systems wherein at least one oxygen, nitrogen or sulfur atom is present as a ring member. Examples are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl and naphthyridinyl.
The above aryl and heteroaryl groups may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time. Examples of substituents of aryl or heteroaryl groups are: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl and phenyl-alkyl, it being possible in turn for all of the preceding groups to carry one or more identical or different halogen atoms; alkoxy; alkenyloxy; alkynyloxy; alkoxyalkyl; halogenalkoxy, alkylthio; halogenalkylthio; alkyl sulfonyl; formyl; alkanoyl; hydroxy; halogen; cyano; nitro; amino; alkylamino; dialkyl amino; carboxy; alkoxycarbonyl; alkenyloxycarbonyl; alkynyloxycarbonyl.
In the above definitions “halogen” or the prefix “halo” includes fluorine, chlorine, bromine and iodine.
The alkyl, alkenyl and alkynyl radicals may be straight-chain or branched. This applies also to the alkyl, alkenyl or alkynyl parts of other alkyl-, alkenyl- or alkynyl-containing groups.
Depending upon the number of carbon atoms mentioned, alkyl on its own or as part of another substituent is to be understood as being, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the isomers thereof, for example isopropyl, isobutyl, tert-butyl or sec-butyl, isopentyl or tert-pentyl.
Cycloalkyl is, depending upon the number of carbon atoms mentioned, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
Depending upon the number of carbon atoms mentioned, alkenyl as a group or as a structural element of other groups is to be understood as being, for example, ethenyl, allyl, 1-propenyl, buten-2-yl, buten-3-yl, penten-1-yl, penten-3-yl, hexen-1-yl, 4-methyl-3-pentenyl or 4-methyl-3-hexenyl.
Alkynyl as a group or as a structural element of other groups is, for example, ethynyl, propyn-1-yl, propyn-2-yl, butyn-1-yl, butyn-2-yl, 1-methyl-2-butynyl, hexyn-1-yl, 1-ethyl-2-butynyl or octyn-1-yl.
A halogenalkyl group may contain one or more (identical or different) halogen atoms, and for example may stand for CHCl2, CH2F, CCl3, CH2Cl, CHF2, CF3, CH2CH2Br, C2Cl5, CH2Br, CHClBr, CF3CH2, etc.
Where R2 and R3 together with the carbon atom to which they are attached form a hydrocarbon ring the ring corresponds to cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane or cyclooctane.
Where R9 and R10 together with the nitrogen atom to which they are attached form a ring system the ring corresponds to pyrrolidine or piperidine.
The presence of at least one asymmetric carbon atom and/or at least one asymmetric oxidized sulfur atom in the compounds of formula I means that the compounds may occur in optically isomeric forms. As a result of the presence of a possible aliphatic C═C double bond, geometric isomerism may also occur. Formula I is intended to include all those possible isomeric forms and mixtures thereof.
Preferred subgroups of compounds of formula I are those wherein
    • n is one; or
    • R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, or C1-C4alkylsulfonyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12halogenalkyl; or a group NR9R10 wherein R9 and R10 are each independently of the other hydrogen or C1-C6alkyl, or together are tetra- or penta-methylene; or
    • R1 is C1-C12alkyl, C2-C12alkenyl; C1-C12halogenalkyl; or a group NR9R10 wherein R9 and R10 are each independently of the other hydrogen or C1-C6alkyl; or
    • R1 is C1-C4alkyl, C2-C4alkenyl; C1-C4halogenalkyl; or C1-C2dialkylamino; or
    • R1 is C1-C4alkyl, vinyl; C1-C4halogenalkyl; or dimethylamino; or
    • R2 is hydrogen and R3 is C1-C8alkyl, C1-C8alkyl optionally substituted by hydroxy, C1-C4-alkoxy, mercapto or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl or C3-C8cycloalkyl-C1-C4alkyl; or
    • R2 is hydrogen and R3 is C1-C4alkyl; C3-C4alkenyl or cyclopropyl; or
    • R2 is hydrogen and R3 is C3-C4alkyl; allyl or cyclopropyl; or
    • R2 is hydrogen and R3 is isopropyl; or
    • R4 is hydrogen, methyl or ethyl; or
    • R4 is hydrogen or methyl; or
    • R4 is hydrogen; or
    • R5, R6 and R7 are each independently hydrogen or methyl; or
    • R5, R6 and R7 are each hydrogen; or
    • R11, R12, R14, R15 and R17 are each independently hydrogen or methyl; or
    • R11, R12, R14, R15 and R17 are each hydrogen; or
    • R13 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur; or
    • R13 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl, benzoxazolyl or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, phenyl, phenyl-C1-C4alkyl wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C1-C8alkoxy-C1-C4alkyl, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, C1-C8alkylsulfonyl, formyl, C2-C8alkanoyl, hydroxy, halogen, cyano, nitro, amino and C1-C8alkylamino, C1-C8dialkylamino, carboxy, C1-C8alkoxycarbonyl, C1-C8alkenyloxycarbonyl and C1-C8alkynyloxycarbonyl; or
    • R13 is C4-C12alkyl; C1-C1-halogenalkyl; C3-C8cycloalkyl; phenyl, naphthyl, thienyl, pyridyl, pyrimidinyl, triazinyl, or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8-alkyl, C2-C8alkenyl, wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; or
    • R13 is C4-C8alkyl; C1-C6halogenalkyl; C3-C8cycloalkyl; phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalkyl, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; or
    • R16 is optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur; or
    • R16 is phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl, benzoxazolyl or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8-cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, phenyl, phenyl-C1-C4alkyl wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C1-C8alkoxy-C1-C4alkyl, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, C1-C8alkylsulfonyl, formyl, C2-C8alkanoyl, hydroxy, halogen, cyano, nitro, amino, C1-C8alkylamino, C1-C8dialkylamino, carboxy, C1-C8alkoxycarbonyl, C1-C8alkenyloxycarbonyl and C1-C8alkynyloxycarbonyl; or
    • R16 is phenyl, naphthyl, thienyl, pyridyl, pyrimidinyl, triazinyl, or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; or
    • R16 is phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalkyl, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8-halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; or
    • Z is oxygen, sulfur or —CH2—; or
    • Z is oxygen.
Further preferred subgroups of the compounds of formula I are those wherein
  • 1) R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, or C1-C4alkylsulfonyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12halogenalkyl; or a group NR9R10 wherein R9 and R10 are each independently of the other hydrogen or C1-C6alkyl, or together are tetra- or penta-methylene;
    • R2 is hydrogen and R3 is C1-C8alkyl; C1-C8alkyl substituted with hydroxy, mercapto, C1-C4alkoxy or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl; C3-C8cycloalkyl-C1-C4alkyl;
    • R13 is C4-C12-alkyl; C1-C12-halogenalkyl; C3-C8cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur; and
    • R16 is optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur; or
  • 2) n is one;
    • R1 is C1-C12alkyl, C2-C12alkenyl; C1-C12halogenalkyl; or a group NR9R10 wherein R9 and R10 are each independently of the other hydrogen or C1-C6alkyl;
    • R2 is hydrogen and R3 is C1-C4alkyl; C3-C4alkenyl or cyclopropyl;
    • R4 is hydrogen, methyl or ethyl; or
    • R5, R6, R7, R11, R12, R14, R15 and R17 are each independently hydrogen or methyl;
    • R13 is C4-C12alkyl; C1-C12-halogenalkyl; C3-C8-cycloalkyl; phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl, benzoxazolyl or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl -C1-C4alkyl, phenyl, phenyl-C1-C4alkyl wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C1-C8alkoxy-C1-C4alkyl, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, C1-C8alkylsulfonyl, formyl, C2-C8alkanoyl, hydroxy, halogen, cyano, nitro, amino and C1-C8alkylamino, C1-C8-dialkylamino, carboxy, C1-C8-alkoxycarbonyl, C1-C8-alkenyloxycarbonyl and C1-C8alkynyloxycarbonyl;
    • R16 is phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl, benzoxazolyl or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8-alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, phenyl, phenyl-C1-C4alkyl wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C1-C8alkoxy-C1-C4alkyl, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, C1-C8alkylsulfonyl, formyl, C2-C8alkanoyl, hydroxy, halogen, cyano, nitro, amino and C1-C8alkylamino, C1-C8dialkylamino, carboxy, C1-C8alkoxycarbonyl, C1-C8alkenyloxycarbonyl and C1-C8alkynyloxycarbonyl; and
    • Z is oxygen, sulfur or —CH2—; or
  • 3) n is one;
    • R1 is C1-C4alkyl, C2-C4alkenyl; C1-C4halogenalkyl; or C1-C2-dialkylamino;
    • R2 is hydrogen and R3 is C3-C4alkyl; allyl or cyclopropyl;
    • R4 is hydrogen or methyl;
    • R5, R6, R7, R11, R12, R14, R15 and R17 are each hydrogen;
    • R13 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; phenyl, naphthyl, thienyl, pyridyl, pyrimidinyl, triazinyl, or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl;
    • R16 is phenyl, naphthyl, thienyl, pyridyl, pyrimidinyl, triazinyl, or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; and
    • Z is oxygen, sulfur or —CH2—; or
  • 4) n is one;
    • R1 is C1-C4alkyl, vinyl; C1-C4halogenalkyl; or dimethylamino;
    • R2 is hydrogen and R3 is isopropyl;
    • R4, R5, R6, R7, R11, R12, R14, R15 and R17 are each hydrogen;
    • R13 is C4-C8alkyl; C1-C6halogenalkyl; C3-C8cycloalkyl; phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalkyl, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8-halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl;
    • R16 is phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalkyl, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; and
    • Z is oxygen.
Preferred individual compounds are:
  • N-(2-{4-[3-(4-chloro-phenyl))-prop-2-ynyloxy]-phenyl}-ethyl)-2-methanesulfonyalmino-3-methyl-butyramide,
  • N-(2-{4-[3-(4-fluoro-phenyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-methanesulfonylamino-3-methyl-butyramide,
  • N-(2-{4-[3-(4-bromo-phenyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-methanesulfonylamino-3-methyl-butyramide,
  • N-(2-{4-[3-(p-tolyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-methanesulfonylamino-3-methyl-butyramide,
  • N-{2-[4-(3-cyclopropyl-prop-2-ynyloxy)-phenyl]-ethyl}-2-methanesulfonylamino-3-methyl-butyramide,
  • N-(2-{4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide,
  • N-(2-{4-[3-(4-fluoro-phenyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide,
  • N-(2-{4-[3-(4-bromo-phenyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide,
  • N-(2-{4-[3-(p-tolyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide, and
  • N-{2-[4-(3-cyclopropyl-prop-2-ynyloxy)-phenyl]-ethyl}-2-ethanesulfonylamino-3-methyl-butyramide.
Certain α-sulfin- and α-sulfonamino acid derivatives having a different kind of molecular structure have already been proposed for controlling plant-destructive fungi (for example in WO 95/030651, WO 97/14677, WO 98/38160, WO 98/38161 and WO 99/07674).
However, the activity of the known compounds is not always satisfactory in all aspects of agricultural needs. Surprisingly, with the compound structure of formula I, a new kind of microbiocides have been found showing an improved systemic activity in plants against phytopathogenic microorganisms, especially fungi.
The α-sulfin- and α-sulfonamino acid amides of formula I may be obtained according to one of the following processes:
a)
Figure US06864392-20050308-C00004
An amino acid of formula II or a carboxy-activated derivative of an amino acid of formula II wherein R1, n, R2 and R3 are as defined for formula I is reacted with an amine of formula III wherein R4, R5, R6, R7 and R8 are as defined above optionally in the presence of a base and optionally in the presence of a diluting agent (step B).
Carboxy-activated derivatives of the amino acid of formula II encompasses all compounds having an activated carboxyl group like an acid halide, such as an acid chloride, like symmetrical or mixed anhydrides, such as mixed anhydrides with O-alkylcarbonates, like activated esters, such as p-nitrophenylesters or N-hydroxysuccinimidesters, as well as in situ produced activated forms of the amino acid of formula II by condensating agents, such as dicyclohexylcarbodiimide, carbonyldiimidazol, benzotriazol-1-yloxy-tris (dimethylamino)phosphonium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-bis(penta methylene)uronium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-bis(tetramethylene)uronium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-tetramethyluronium hexafluoro-phosphate or benzotriazol-1-yloxy-tripyrrolidino phosphonium hexafluorophosphate. The mixed anhydrides of the amino acids of the formula II may be prepared by reaction of an amino acid of formula II with chloroformic acid esters like chloroformic acid alkylesters, such as ethyl chloroformate or isobutyl chloroformate, optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine.
The present reaction is preferably performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; amides, e.g. N,N-dimethylformamide; nitriles e.g. acetonitrile; or ethers e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is also possible to use mixtures of these solvents. The reaction is preformed optionally in the presence of an organic or inorganic base like a tertiary amine, e.g. triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from −80° C. to +150° C., preferentially at temperatures ranging from −40° C. to +40° C.
The compounds of formula II may be prepared by reaction of an amino acid of formula IV where R2 and R3 are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V where R1 and n have the same meanings as defined above and where X is halide, preferentially chlorine or bromine (step A).
The reaction may be performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons, e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is also possible to use mixtures of these solvents. The reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from −80° C. to +150° C., preferentially at temperatures ranging from −40° C. to +40° C.
b)
Figure US06864392-20050308-C00005
The compounds of formula I may also be prepared by reaction of an amino acid derivative of formula VI wherein R2, R3, R4, R5, R6, R7 and R8 are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V wherein R1 and n are as defined for formula I and X is halide, preferentially chlorine or bromine (step C). The reaction is performed in the same manner as described for step A.
c)
Figure US06864392-20050308-C00006
The compounds of formula I may also be prepared by reaction of a phenol of formula VII wherein R1, n, R2, R3, R4, R5, R6 and R7 are as defined for formula I with a compound of formula VIII wherein R8 is as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate (step D). The reaction may be performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones e.g. acetone or 2-butanone; esters, e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane, amides, e.g. dimethylformamide, nitriles, e.g. acetonitrile, alcohols, e.g. methanol, ethanol, isopropanol, n-butanol or tert-butanol, sulfoxides e.g. dimethylsulfoxide or water. It is also possible to use mixtures of these solvents. The reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide, a metal carbonate or a metal alkoxide, preferentially an alkali hydroxide, an alkali carbonate or an alkali alkoxide, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide or potassium tert-butoxide at temperatures ranging from −80° C. to +200° C., preferentially at temperatures ranging from 0° C. to +120° C.
d)
Figure US06864392-20050308-C00007
The compounds of formula Ia may also be prepared via formula IX wherein R1, n, R2, R3, R4, R5, R6, R7, R11, R12 and R13 are defined for formula I by reacting of a phenol of formula VII wherein R1, n, R2, R3, R4, R5, R6 and R7 are as defined for formula I with a compound of formula VIIIa wherein R11, R12 and R13 are as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate (step E).
The reaction is performed in the same manner as described for step D.
The compounds of formula Ia R11, R12 and R13 is as defined for formula I may be prepared by reaction of compounds of formula IX with hydrogen.
The reaction is performed in a solvent like ethers, e.g. diethylether, dioxane or tetrahydrofuran, or like alcohols, e.g. methanol or ethanol, or water in the presence of transition metals or transition metal salts, e.g. nickel, cobalt, palladium, platinum or rhodium, optionally in the presence of bases, e.g. ammonia, or in the presence of salts, e.g. barium sulfate, at temperatures ranging from −20° C. to +160° C. and at pressures ranging from 1 to 200 bar.
aa) The intermediate amines of formula III may be obtained by one of the following processes:
Figure US06864392-20050308-C00008
Figure US06864392-20050308-C00009
Step 1 is the alkylation of a phenol with a compound of formula VIII. The reaction is performed in the same manner as described for procedure c).
Step 2 is the reaction of an aromatic aldehyde with nitromethane. This reaction is performed in a solvent like an organic carboxylic acids, e.g. acetic acid optionally in the presence of the ammonium salt of this carboxylic acid, e.g. ammonium acetate at temperatures ranging from 0° C. to +200° C.
Step 3 is the reduction of an unsaturated nitrogen-compound. This reaction is performed in a solvent like an ether, e.g. diethylether, dioxane or tetrahydrofuran, or an alcohol, e.g. methanol, ethanol or isopropanol, with borohydride, with a boron-complex, e.g. the complex of borohydride with tetrahyrofuran, with an alkaliborohydride, with an alkalialuminiumhydride, e.g. lithiumaluminiumhydride, with aluminiumhydride, with an aluminiumalkoxyhydride or with hydrogen optionally in the presence of a transition metal, a transition metal salt or a transition metal complex, e.g. nickel, cobalt, palladium, platinium or rhodium at temperatures ranging from −50° C. to +200° C.
Step 4 is the reaction of an aldehyde or a ketone of formula XXIII with hydroxylamine or with a salt of hydroxylamine. This reaction is performed in a solvent like an alcohol, e.g. methanol, ethanol or isopropanol, like an ether, e.g. diethylether, dioxane or tetrahydrofuran, like an amide, e.g. dimethylformamide, or in water or in a mixture of these solvents optionally in the presence of an organic or inorganic base like a tertiary amine, e.g. triethylamine, like a heterocyclic compound containing nitrogen, e.g. pyridine, or like an alkalicarbonate, e.g. sodium carbonate or potassium carbonate, at temperatures ranging from −20° C. to +150° C.
Step 5 is the exchange of hydroxy by cyanide. This reaction is performed in an organic solvent like an amide, e.g. dimethylformamide using a metal cyanide like an alkali cyanide, e.g. sodium cyanide or potassium cyanide, at temperatures ranging from 0° C. to +200° C.
Step 6 is the hydrolysis of an alkyl ester. This reaction is performed in a solvent like an alcohol, e.g. methanol, ethanol or isopropanol, like an ether, e.g. diethylether, dioxane or tetrahydrofuran, like a halogenated hydrocarbon, e.g. dichloromethane, or water or in a mixture of these solvents optionally in the presence of an alkali hydroxide, e.g. lithium hydroxide, sodium hydroxide or potassium hydroxide, or optionally in the presence of an acid, e.g. hydrogen chloride, sulfuric acid or trifluoroacetic acid at temperatures ranging from −20° C. to +160° C.
Step 7 is the reaction of a carboxylic acid or the activated form of this carboxylic acid with hydrogen azide or an azide-salt. An activated form of a carboxylic acid can be the acid halogenide, e.g. acid chloride, a symmetric or a mixed anhydride. Azide-salts can be alkali azides, e.g. sodium azide. The reaction is performed in a solvent like a hydrocarbon, e.g. toluene or xylene, like a halogenated hydrocarbon, e.g. chloroform, like an ether, e.g. dioxane, like a ketone, e.g. acetone or 2-butanone, like an alcohol, e.g. methanol, ethanol or tert-butanol, or water or in a mixture of these solvents optionally in the presence of an acid like an inorganic acid, e.g. sulfuric acid or hydrogen chloride at temperatures ranging from −40° C. to +200° C.
In a preferred form the compounds of formula XXVI are prepared starting from compounds of the formula XXV by applying step 5 and step 1 in the same pot.
bb) Amines of formula VI can be obtained by the following process:
Figure US06864392-20050308-C00010
wherein R is lower alkyl or optionally substituted benzyl.
Step 8 is the amidation of an carbamate-protected amino acid of formula XXXIII with an amine of formula XXXIV. The reaction is performed in the same manner as described for step A.
Step 9 is the alkylation of a phenol of formula XXXV with an compound of formula VIII. The reaction is performed in the same manner as described for step D.
Step 10 is the hydrolysis of a carbamate of formula XXXVI. The reaction is performed in a solvent like hydrocarbons, e.g. toluene, like halogenated hydrocarbons, e.g. dichloromethane, like ketones, e.g. acetone, like esters, e.g. ethyl acetate, like ethers, e.g. dioxane or tetrahydrofuran, or like water or in mixtures of these solvents optionally in the presence of an organic acid like carboxylic acid, e.g. trifluoroacetic acid, or like a sulfonic acid, e.g. methanesulfonic acid or toluenesulfonic acid, or in the presence of an inorganic acid, e.g. hydrogen chloride or sulfuric acid, at temperatures ranging from −40° C. to +160° C.
The compounds of formula I are oils or solids at room temperature and are distinguished by valuable microbiocidal properties. They can be used in the agricultural sector or related technical fields preventively and curatively for the control of plant-destructive microorganisms. The compounds of formula I according to the invention are distinguished at low rates of concentration not only by outstanding microbiocidal, especially fungicida I, activity but also by being especially well tolerated by the treated crop plants.
Surprisingly, it has now been found that for practical purposes the compounds of formula I have a very advantageous biocidal spectrum in the control of phytopathogenic microorganisms, especially fungi. With the compounds of formula I it is possible to inhibit or destroy phytopathogenic microorganisms that occur on various crops of useful plants or on parts of such plants (fruit, blossom, leaves, stems, tubers, roots), while parts of the plants which grow later also remain protected, for example, against phyto pathogenic fungi.
The novel compounds of formula I prove to be effective against specific genera of the fungus classes Fungi imperfecti (e.g. Cercospora), Basidio mycetes (e.g. Puccinia) and Ascomycetes (e.g. Erysiphe and Venturia) and especially against Oomycetes (e.g. Plasmopara, Peronospora, Pythium and Phytophthora). They therefore represent in plant protection a valuable addition to the compositions for controlling phyto pathogenic fungi. The compounds of formula I can also be used as coatings or dressings for protecting seed (fruit, tubers, grains) and plant cuttings from fungal infections and against phyto pathogenic fungi that occur in the soil.
The invention relates also to compositions comprising compounds of formula I as active ingredient, especially plant-protecting compositions, and to the use thereof in the agricultural sector or related fields.
In addition, the present invention includes the preparation of those compositions, wherein the active ingredient is homogeneously mixed with one or more of the substances or groups of substances described herein. Also included is a method of treating plants which is distinguished by the application of the novel compounds of formula I or of the novel compositions.
Target crops to be protected within the scope of this invention comprise, for example, the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucurbitaceae (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamon, camphor) and plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, and also ornamentals.
The compounds of formula I are normally used in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with other active ingredients. Those other active ingredients may be fertilisers, micronutrient donors or other preparations that influence plant growth. It is also possible to use selective herbicides or insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of those preparations, if desired together with further carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology.
The compounds of formula I can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities.
Mixing components which are particularly preferred are azoles such as azoles, such as azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinyl carbinols, such as ancymidol, fenarimol, nuarimol; 2-amino-pyrimidines, such as bupirimate, dimethirimol, ethirimol; morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil; pyrroles, such as fenpiclonil, fludioxonil; phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl; benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole; dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozolin; carboxamides, such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, thifluzamide; guanidines, such as guazatine, dodine, iminoctadine; strobilurines, such as azoxystrobin, kresoxim-methyl, metominostrobin, SSF-129, CGA 279202 (trifloxystrobin), picoxystrobin; dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halogenmethylthiophthalimides, such as captafol, captan, dichlofluanid, fluoromide, folpet, tolyfluanid; Cu compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper; nitrophenol derivatives, such as dinocap, nitrothal-isopropyl; organo-P derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl; various, such as AC382042, acibenzolar-S-methyl, anilazine, blasticidin-S, quinomethionat, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, fenamidone, fenhexamid, fentin, ferimzone, fluazinam, flusulfamide, fosetyl-aluminium, hymexazol, IKF-916, iprovalicarb, kasugamycin, methasulfocarb, MON65500, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, RH-7281, RPA 407213, BAS 50001 F, sulfur, SYP-Z071, triazoxide, tricyclazole, triforine, validamycin.
Suitable carriers and surfactants may be solid or liquid and correspond to the substances ordinarily employed in formulation technology, such as e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers. Such carriers and additives are described, for example, in WO 95/30651.
A preferred method of applying a compound of formula I, or an agrochemical composition comprising at least one of those compounds, is application to the foliage (foliar application), the frequency and the rate of application depending upon the risk of infestation by the pathogen in question. The compounds of formula I may also be applied to seed grains (coating) either by impregnating the grains with a liquid formulation of the active ingredient or by coating them with a solid formulation.
The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and are for that purpose advantageously formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and by encapsulation in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
Advantageous rates of application are normally from 1 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, especially from 25 g to 750 g a.i./ha. When used as seed dressings, rates of from 0.001 g to 1.0 g of active ingredient per kg of seed are advantageously used.
The formulations, i.e. the compositions, preparations or mixtures comprising the compound(s) (active ingredient(s)) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
Further surfactants customarily used in formulation technology will be known to the person skilled in the art or can be found in the relevant technical literature.
The agrochemical compositions usually comprise 0.01 to 99% by weight, preferably 0.1 to 95% by weight, of a compound of formula I, 99.99 to 1% by weight, preferably 99.9 to 5% by weight, of a solid or liquid adjuvant, and 0 to 25% by weight, preferably 0.1 to 25% by weight, of a surfactant.
Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
The compositions may also comprise further ingredients, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.
The Examples which follow illustrate the invention described above, without limiting the scope thereof in any way. Temperatures are given in degrees Celsius.
PREPARATION EXAMPLES FOR COMPOUNDS OF FORMULA I Example A1.1 (S)-2-Ethanesulfonylamino-N-(2-{4-[3-(4-chloro-phenyl)-propargyloxy]-phenyl}-ethyl)-3-methyl-butyramide
Figure US06864392-20050308-C00011
A mixture of 1.0 g of (S)-2-ethanesulfonylamino-N-[2-(4-hydroxy-phenyl)-ethyl]-3-methyl-butyramide, 1.3 g of toluene-4-sulfonic acid 3-(4-chloro-phenyl)-prop-2-ynyl ester and 4.9 ml of a 1M solution of sodium methoxide in methanol in 25 ml of methanol is heated to reflux for 2 hours. After cooling 200 ml of water is added. The mixture is extracted with ethyl acetate (2×300 ml). The organic layers are washed with brine (2×100 ml), combined, dried (MgSO4) and evaporated. (S)-N-(2-{4-[3-(4-Chloro-phenyl)-propargyloxy]-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide is obtained which is purified by recrystallization (ethyl acetate/hexane), m.p. 141-142° C.
Analogously to example A1.1 the compounds listed in table A1 are obtained.
    • *) Configuration on the α-C-atom in the amino acid moiety; Ph means phenyl
TABLE A1
Figure US06864392-20050308-C00012
No R1 *) R3 R4 R8 m.p. (° C.)
A1.1 CH3—CH2— (S) (CH3)2CH— H (4-Cl—Ph)—C≡C—CH2— 141-142
A1.2 CH3—CH2— (S) (CH3)2CH— H (4-F—Ph)—C≡C—CH2— 133-134
A1.3 CH3 (S) (CH3)2CH— H (4-Cl—Ph)—C≡C—CH2— 154-155
A1.4 CH3 (S) (CH3)2CH— H (4-F—Ph)—C≡C—CH2— 104-105
A1.5 CH3 (S) (CH3)2CH— H (4-Br—Ph)—C≡C—CH2— 161-164
A1.6 CH3 (S) (CH3)2CH— H (4-CH3-Ph)—C≡C—CH 2— 110-112
A1.7 CH3 (S) (CH3)2CH— H (4-Cl—Ph)—CH═CH—CH2— 144-145
A1.8 CH3 (S) (CH3)2CH— H (4-Cl—Ph)—CH2—CH2—CH2— 176-177
A1.9 CH3 (S) (CH3)2CH— H (3-CF3—Ph)—CH2 147-153
Example A2.1 (S)-2-Ethanesulfonylamino-N-[2-(4-hydroxy-phenyl)-ethyl]-3-methyl-butyramide
Figure US06864392-20050308-C00013
18.6 g of (S)-N-[2-(4-benzyloxy-phenyl)-ethyl]-2-ethanesulfonylamino-3-methyl-butyramide and 16.8 g of palladium (5% on charcoal) in 400 ml of tetrahydrofuran are shaken under a hydrogen atmosphere at +30 to +−35° C. and at normal pressure for 5 hours. The reaction mixture is filtered and evaporated. (S)-2-ethanesulfonylamino-N-[2-(4-hydroxy-phenyl)-ethyl]-3-methyl-butyramide is obtained in form of an oil [MS (m/e): 329 (M+H)+].
Analogously to example A2.1 the compounds listed in table A2 are obtained.
    • *) Configuration on the α-C-atom in the amino acid moiety; Ph means phenyl
TABLE A2
Figure US06864392-20050308-C00014
No R1 *) R3 R4 m.p. (° C.)
A2.1 CH3—CH2— (S) (CH3)2CH— H Oil
A2.2 CH3 (S) (CH3)2CH— H 120-121
*) Configuration of the amino acid moiety
Example A3.1 (S)-N-[2-(4-Benzyloxy-phenyl)-ethyl]-2-ethanesulfonylamino-3-methyl-butyramide
Figure US06864392-20050308-C00015
15 g of (S)-2-ethanesulfonylamino-3-methyl-butyric acid, 10.3 g of thionyl chloride and N,N-dimethylformamide (2 drops) in toluene (75 ml) are refluxed for 2 hours. The solvent is then evaporated. To the resulting residue 100 ml of toluene is added. The mixture is then evaporated to dryness again. The residue is dissolved in dioxane (100 ml) and added to a mixture of 2-(4-benzyloxy-phenyl)-ethylamine (15.3 g) and triethylamine (7.2 g) in dioxane (100 ml). The reaction mixture is stirred at room temperature over night. Water (400 ml) is added. It is extracted with ethyl acetate (2×500 ml). The organic layers are washed with hydrochloric acid (80 ml, 1M solution) and brine (2×100 ml), dried (MgSO4) and evaporated. (S)-N-[2-(4-Benzyloxy-phenyl)-ethyl]-2-ethanesulfonylamino-3-methyl-butyramide which is purified by recrystallization (ethyl acetate/hexane), m.p. 133-134° C.
Analogously to example A3.1 the compounds listed in table A3 are obtained.
    • *) Configuration on the α-C-atom in the amino acid moiety; Ph means phenyl
TABLE A3
Figure US06864392-20050308-C00016
No R1 *) R3 R4 m.p. (° C.)
A3.1 CH3—CH2— (S) (CH3)2CH— H 133-134
A3.2 CH3 (S) (CH3)2CH— H 153-154
*) Configuration of the amino acid moiety
Analogously to the above Examples the following compounds of Tables 1 to 13 may be prepared. In the tables Ph means phenyl.
TABLE 1
Compounds represented by the Formula I.1 where the combination
of the groups R1, R3 and R8 corresponds
to each row in table A.
I.1
Figure US06864392-20050308-C00017
TABLE 2
Compounds represented by the Formula I.2 where the combination
of the groups R1, R3 and R8 corresponds
to each row in table A.
I.2
Figure US06864392-20050308-C00018
TABLE 3
Compounds represented by the Formula I.3 where the combination
of the groups R1, R3 and R8 corresponds
to each row in table A.
I.3
Figure US06864392-20050308-C00019
TABLE 4
Compounds represented by the Formula I.4 where the combination
of the groups R1, R3 and R8 corresponds
to each row in table A.
I.4
Figure US06864392-20050308-C00020
TABLE 5
Compounds represented by the Formula I.5 where the combination
of the groups R1, R3 and R8 corresponds
to each row in table A.
I.5
Figure US06864392-20050308-C00021
TABLE 6
Compounds represented by the Formula I.6 where the combination
of the groups R1, R3 and R8 corresponds to each
row in table A.
I.6
Figure US06864392-20050308-C00022
TABLE A
No. R1 R3 R8
001 CH3— CH3—CH2— CH3—(CH2 )3—C≡C—CH2—
002 CH3—CH2— CH3—CH2— CH3—(CH2 )3—C≡C—CH2—
003 (CH3)2N— CH3—CH2— CH3—(CH2 )3—C≡C—CH2—
004 CH3—CH2—CH2— CH3—CH2— CH3—(CH2 )3—C≡C—CH2—
005 (CH3)2CH— CH3—CH2— CH3—(CH2 )3—C≡C—CH2—
006 Cl—CH2—CH2—CH2— CH3—CH2— CH3—(CH2 )3—C≡C—CH2—
007 CH3— (CH3)2CH— CH3—(CH2 )3—C≡C—CH2—
008 CH3—CH2— (CH3)2CH— CH3—(CH2 )3—C≡C—CH2—
009 (CH3)2N— (CH3)2CH— CH3—(CH2 )3—C≡C—CH2—
010 CH3—CH2—CH2— (CH3)2CH— CH3—(CH2 )3—C≡C—CH2—
011 (CH3)2CH— (CH3)2CH— CH3—(CH2 )3—C≡C—CH2—
012 Cl—CH2—CH2—CH2— (CH3)2CH— CH3—(CH2 )3—C≡C—CH2—
013 CH3— CH3—CH2—CH2— CH3—(CH2 )3—C≡C—CH2—
014 CH3—CH2— CH3—CH2—CH2— CH3—(CH2 )3—C≡C—CH2—
015 (CH3)2N— CH3—CH2—CH2— CH3—(CH2 )3—C≡C—CH2—
016 CH3—CH2—CH2— CH3—CH2—CH2— CH3—(CH2 )3—C≡C—CH2—
017 (CH3)2CH— CH3—CH2—CH2— CH3—(CH2 )3—C≡C—CH2—
018 Cl—CH2—CH2—CH2— CH3—CH2—CH2— CH3—(CH2 )3—C≡C—CH2—
019 CH3—
Figure US06864392-20050308-C00023
 		CH3—(CH2 )3—C≡C—CH2—
020 CH3—CH2—
Figure US06864392-20050308-C00024
 		CH3—(CH2 )3—C≡C—CH2—
021 (CH3)2N—
Figure US06864392-20050308-C00025
 		CH3—(CH2 )3—C≡C—CH2—
022 CH3—CH2—CH2—
Figure US06864392-20050308-C00026
 		CH3—(CH2 )3—C≡C—CH2—
023 (CH3)2CH—
Figure US06864392-20050308-C00027
 		CH3—(CH2 )3—C≡C—CH2—
024 Cl—CH2—CH2—CH2—
Figure US06864392-20050308-C00028
 		CH3—(CH2 )3—C≡C—CH2—
025 CH3— CH2═CH—CH2— CH3—(CH2 )3—C≡C—CH2—
026 CH3—CH2— CH2═CH—CH2— CH3—(CH2 )3—C≡C—CH2—
027 (CH3)2N— CH2═CH—CH2— CH3—(CH2 )3—C≡C—CH2—
028 CH3—CH2—CH2— CH2═CH—CH2— CH3—(CH2 )3—C≡C—CH2—
029 (CH3)2CH— CH2═CH—CH2— CH3—(CH2 )3—C≡C—CH2—
030 Cl—CH2—CH2—CH2— CH2═CH—CH2— CH3—(CH2 )3—C≡C—CH2—
031 CH3— CH═C—CH2— CH3—(CH2 )3—C≡C—CH2—
032 CH3—CH2— CH═C—CH2— CH3—(CH2 )3—C≡C—CH2—
033 (CH3)2N— CH═C—CH2— CH3—(CH2 )3—C≡C—CH2—
034 CH3—CH2—CH2— CH═C—CH2— CH3—(CH2 )3—C≡C—CH2—
035 (CH3)2CH— CH═C—CH2— CH3—(CH2 )3—C≡C—CH2—
036 Cl—CH2—CH2—CH2— CH═C—CH2— CH3—(CH2 )3—C≡C—CH2—
037 CH3— CH3—CH2—CH(CH3)— CH3—(CH2 )3—C≡C—CH2—
038 CH3—CH2— CH3—CH2—CH(CH3)— CH3—(CH2 )3—C≡C—CH2—
039 (CH3)2N— CH3—CH2—CH(CH3)— CH3—(CH2 )3—C≡C—CH2—
040 CH3—CH2—CH2— CH3—CH2—CH(CH3)— CH3—(CH2 )3—C≡C—CH2—
041 (CH3)2CH— CH3—CH2—CH(CH3)— CH3—(CH2 )3—C≡C—CH2—
042 Cl—CH2—CH2—CH2— CH3—CH2—CH(CH3)— CH3—(CH2 )3—C≡C—CH2—
045 CH3— CH3—CH2—
Figure US06864392-20050308-C00029
046 CH3—CH2— CH3—CH2—
Figure US06864392-20050308-C00030
047 (CH3)2N— CH3—CH2—
Figure US06864392-20050308-C00031
048 CH3—CH2—CH2— CH3—CH2—
Figure US06864392-20050308-C00032
049 (CH3)2CH— CH3—CH2—
Figure US06864392-20050308-C00033
050 Cl—CH2—CH2—CH2— CH3—CH2—
Figure US06864392-20050308-C00034
51 CH3— (CH3)2CH—
Figure US06864392-20050308-C00035
052 CH3—CH2— (CH3)2CH—
Figure US06864392-20050308-C00036
053 (CH3)2N— (CH3)2CH—
Figure US06864392-20050308-C00037
054 CH3—CH2—CH2— (CH3)2CH—
Figure US06864392-20050308-C00038
055 (CH3)2CH— (CH3)2CH—
Figure US06864392-20050308-C00039
056 Cl—CH2—CH2—CH2— (CH3)2CH—
Figure US06864392-20050308-C00040
057 CH3— CH3—CH2—CH2—
Figure US06864392-20050308-C00041
058 CH3—CH2— CH3—CH2—CH2—
Figure US06864392-20050308-C00042
059 (CH3)2N— CH3—CH2—CH2—
Figure US06864392-20050308-C00043
060 CH3—CH2—CH2— CH3—CH2—CH2—
Figure US06864392-20050308-C00044
061 (CH3)2CH— CH3—CH2—CH2—
Figure US06864392-20050308-C00045
062 Cl—CH2—CH2—CH2— CH3—CH2—CH2—
Figure US06864392-20050308-C00046
063 CH3—
Figure US06864392-20050308-C00047
Figure US06864392-20050308-C00048
064 CH3—CH2—
Figure US06864392-20050308-C00049
Figure US06864392-20050308-C00050
065 (CH3)2N—
Figure US06864392-20050308-C00051
Figure US06864392-20050308-C00052
066 CH3—CH2—CH2—
Figure US06864392-20050308-C00053
Figure US06864392-20050308-C00054
067 (CH3)2CH—
Figure US06864392-20050308-C00055
Figure US06864392-20050308-C00056
068 Cl—CH2—CH2—CH2—
Figure US06864392-20050308-C00057
Figure US06864392-20050308-C00058
069 CH3— CH2═CH—CH2—
Figure US06864392-20050308-C00059
070 CH3—CH2— CH2═CH—CH2—
Figure US06864392-20050308-C00060
071 (CH3)2N— CH2═CH═CH2—
Figure US06864392-20050308-C00061
072 CH3—CH2—CH2— CH2═CH—CH2—
Figure US06864392-20050308-C00062
073 (CH3)2CH— CH2═CH—CH2—
Figure US06864392-20050308-C00063
074 Cl—CH2—CH2—CH2— CH2═CH—CH2—
Figure US06864392-20050308-C00064
075 CH3— CH═C—CH2—
Figure US06864392-20050308-C00065
076 CH3—CH2— CH≡C—CH2—
Figure US06864392-20050308-C00066
077 (CH3)2N— CH≡C—CH2—
Figure US06864392-20050308-C00067
078 CH3—CH2—CH2— CH≡C—CH2—
Figure US06864392-20050308-C00068
079 (CH3)2CH— CH≡C—CH2—
Figure US06864392-20050308-C00069
080 Cl—CH2—CH2—CH2— CH≡C—CH2—
Figure US06864392-20050308-C00070
081 CH3— CH3—CH2—CH(CH3)—
Figure US06864392-20050308-C00071
082 CH3—CH2— CH3—CH2—CH(CH3)—
Figure US06864392-20050308-C00072
083 (CH3)2N— CH3—CH2—CH(CH3)—
Figure US06864392-20050308-C00073
084 CH3—CH2—CH2— CH3—CH2—CH(CH3)—
Figure US06864392-20050308-C00074
085 (CH3)2CH— CH3—CH2—CH(CH3)—
Figure US06864392-20050308-C00075
086 Cl—CH2—CH2—CH2— CH3—CH2—CH(CH3)—
Figure US06864392-20050308-C00076
087 CH3— CH3—CH2— Ph—C≡C—CH2—
088 CH3—CH2— CH3—CH2— Ph—C≡C—CH2—
089 (CH3)2N— CH3—CH2— Ph—C≡C—CH2—
090 CH3—CH2—CH2— CH3—CH2— Ph—C≡C—CH2—
091 (CH3)2CH— CH3—CH2— Ph—C≡C—CH2—
092 Cl—CH2—CH2—CH2— CH3—CH2— Ph—C≡C—CH2—
093 CH3— (CH3)2CH— Ph—C≡C—CH2—
094 CH3—CH2— (CH3)2CH— Ph—C≡C—CH2—
095 (CH3)2N— (CH3)2CH— Ph—C≡C—CH2—
096 CH3—CH2—CH2— (CH3)2CH— Ph—C≡C—CH2—
097 (CH3)2CH— (CH3)2CH— Ph—C≡C—CH2—
098 Cl—CH2—CH2—CH2— (CH3)2CH— Ph—C≡C—CH2—
099 CH3— CH3—CH2—CH2— Ph—C≡C—CH2—
100 CH3—CH2— CH3—CH2—CH2— Ph—C≡C—CH2—
101 (CH3)2N— CH3—CH2—CH2— Ph—C≡C—CH2—
102 CH3—CH2—CH2— CH3—CH2—CH2— Ph—C≡C—CH2—
103 (CH3)2CH— CH3—CH2—CH2— Ph—C≡C—CH2—
104 Cl—CH2—CH2—CH2— CH3—CH2—CH2— Ph—C≡C—CH2—
105 CH3—
Figure US06864392-20050308-C00077
 		Ph—C≡C—CH2—
106 CH3—CH2—
Figure US06864392-20050308-C00078
 		Ph—C≡C—CH2—
107 (CH3)2N—
Figure US06864392-20050308-C00079
 		Ph—C≡C—CH2—
108 CH3—CH2—CH2—
Figure US06864392-20050308-C00080
 		Ph—C≡C—CH2—
109 (CH3)2CH—
Figure US06864392-20050308-C00081
 		Ph—C≡C—CH2—
110 Cl—CH2—CH2—CH2—
Figure US06864392-20050308-C00082
 		Ph—C≡C—CH2—
111 CH3— CH2═CH—CH2— Ph—C≡C—CH2—
112 CH3—CH2— CH2═CH—CH2— Ph—C≡C—CH2—
113 (CH3)2N— CH2═CH—CH2— Ph—C≡C—CH2—
114 CH3—CH2—CH2— CH2═CH—CH2— Ph—C≡C—CH2—
115 (CH3)2CH— CH2═CH—CH2— Ph—C≡C—CH2—
116 Cl—CH2—CH2—CH2— CH2═CH—CH2— Ph—C≡C—CH2—
117 CH3— CH≡C—CH2— Ph—C≡C—CH2—
118 CH3—CH2— CH≡C—CH2— Ph—C≡C—CH2—
119 (CH3)2N— CH≡C—CH2— Ph—C≡C—CH2—
120 CH3—CH2—CH2— CH≡C—CH2— Ph—C≡C—CH2—
121 (CH3)2CH— CH≡C—CH2— Ph—C≡C—CH2—
122 Cl—CH2—CH2—CH2— CH≡C—CH2— Ph—C≡C—CH2—
123 CH3— CH3—CH2—CH(CH3)— Ph—C≡C—CH2—
124 CH3—CH2— CH3—CH2—CH(CH3)— Ph—C≡C—CH2—
125 (CH3)2N— CH3—CH2—CH(CH3)— Ph—C≡C—CH2—
126 CH3—CH2—CH2— CH3—CH2—CH(CH3)— Ph—C≡C—CH2—
127 (CH3)2CH— CH3—CH2—CH(CH3)— Ph—C≡C—CH2—
128 Cl—CH2—CH2—CH2— CH3—CH2—CH(CH3)— Ph—C≡C—CH2—
129 CH3— CH3—CH2— (4—F—Ph)—C≡C—CH2—
130 CH3—CH2— CH3—CH2— (4-F—Ph)—C≡C—CH2—
131 (CH3)2N— CH3—CH2— (4-F—Ph)—C≡C—CH2—
132 CH3—CH2—CH2— CH3—CH2— (4-F—Ph)—C≡C—CH2—
133 (CH3)2CH— CH3—CH2— (4-F—Ph)—C≡C—CH2—
134 Cl—CH2—CH2—CH2— CH3—CH2— (4-F—Ph)—C≡C—CH2—
135 CH3— (CH3)2CH2— (4-F—Ph)—C≡C—CH2—
136 CH3—CH2— (CH3)2CH2— (4-F—Ph)—C≡C—CH2—
137 (CH3)2N— (CH3)2CH2— (4-F—Ph)—C≡C—CH2—
138 CH3—CH2—CH2— (CH3)2CH2— (4-F—Ph)—C≡C—CH2—
139 (CH3)2CH— (CH3)2CH2— (4-F—Ph)—C≡C—CH2—
140 Cl—CH2—CH2—CH2— (CH3)2CH2— (4-F—Ph)—C≡C—CH2—
141 CH3— CH3—CH2—CH2— (4-F—Ph)—C≡C—CH2—
142 CH3—CH2— CH3—CH2—CH2— (4-F—Ph)—C≡C—CH2—
143 (CH3)2N— CH3—CH2—CH2— (4-F—Ph)—C≡C—CH2—
144 CH3—CH2—CH2— CH3—CH2—CH2— (4-F—Ph)—C≡C—CH2—
145 (CH3)2CH— CH3—CH2—CH2— (4-F—Ph)—C≡C—CH2—
146 Cl—CH2—CH2—CH2— CH3—CH2—CH2— (4-F—Ph)—C≡C—CH2—
147 CH3—
Figure US06864392-20050308-C00083
 		(4-F—Ph)—C≡C—CH2—
148 CH3—CH2—
Figure US06864392-20050308-C00084
 		(4-F—Ph)—C≡C—CH2—
149 (CH3)2N—
Figure US06864392-20050308-C00085
 		(4-F—Ph)—C≡C—CH2—
150 CH3—CH2—CH2—
Figure US06864392-20050308-C00086
 		(4-F—Ph)—C≡C—CH2—
151 (CH3)2CH—
Figure US06864392-20050308-C00087
 		(4-F—Ph)—C≡C—CH2—
152 Cl—CH2—CH2—CH2—
Figure US06864392-20050308-C00088
 		(4-F—Ph)—C≡C—CH2—
153 CH3— CH2═CH—CH2— (4-F—Ph)—C≡C—CH2—
154 CH3—CH2— CH2═CH—CH2— (4-F—Ph)—C≡C—CH2—
155 (CH3)2N— CH2═CH—CH2— (4-F—Ph)—C≡C—CH2—
156 CH3—CH2—CH2— CH2═CH—CH2— (4-F—Ph)—C≡C—CH2—
157 (CH3)2CH— CH2═CH—CH2— (4-F—Ph)—C≡C—CH2—
158 Cl—CH2—CH2—CH2— CH2═CH—CH2— (4-F—Ph)—C≡C—CH2—
159 CH3— CH≡C—CH2— (4-F—Ph)—C≡C—CH2—
160 CH3—CH2— CH≡C—CH2— (4-F—Ph)—C≡C—CH2—
161 (CH3)2N— CH≡C—CH2— (4-F—Ph)—C≡C—CH2—
162 CH3—CH2—CH2— CH≡C—CH2— (4-F—Ph)—C≡C—CH2—
163 (CH3)2CH— CH≡C—CH2— (4-F—Ph)—C≡C—CH2—
164 Cl—CH2—CH2—CH2— CH≡C—CH2— (4-F—Ph)—C≡C—CH2—
165 CH3— CH3—CH2—CH(CH3)— (4-F—Ph)—C≡C—CH2—
166 CH3—CH2— CH3—CH2—CH(CH3)— (4-F—Ph)—C≡C—CH2—
167 (CH3)2N— CH3—CH2—CH(CH3)— (4-F—Ph)—C≡C—CH2—
168 CH3—CH2—CH2— CH3—CH2—CH(CH3)— (4-F—Ph)—C≡C—CH2—
169 (CH3)2CH— CH3—CH2—CH(CH3)— (4-F—Ph)—C≡C—CH2—
170 Cl—CH2—CH2—CH2— CH3—CH2—CH(CH3)— (4-F—Ph)—C≡C—CH2—
171 CH3— CH3—CH2— (4-Cl—Ph)—C≡C—CH2—
172 CH3—CH2— CH3—CH2— (4-Cl—Ph)—C≡C—CH2—
173 (CH3)2N— CH3—CH2— (4-Cl—Ph)—C≡C—CH2—
174 CH3—CH2—CH2— CH3—CH2— (4-Cl—Ph)—C≡C—CH2—
175 (CH3)2CH— CH3—CH2— (4-Cl—Ph)—C≡C—CH2—
176 Cl—CH2—CH2—CH2— CH3—CH2— (4-Cl—Ph)—C≡C—CH2—
177 CH3— (CH3)2CH— (4-Cl—Ph)—C≡C—CH2—
178 CH3—CH2— (CH3)2CH— (4-Cl—Ph)—C≡C—CH2—
179 (CH3)2N— (CH3)2CH— (4-Cl—Ph)—C≡C—CH2—
180 CH3—CH2—CH2— (CH3)2CH— (4-Cl—Ph)—C≡C—CH2—
181 (CH3)2CH— (CH3)2CH— (4-Cl—Ph)—C≡C—CH2—
182 Cl—CH2—CH2—CH2— (CH3)2CH— (4-Cl—Ph)—C≡C—CH2—
183 CH3— CH3—CH2—CH2— (4-Cl—Ph)—C≡C—CH2—
184 CH3—CH2— CH3—CH2—CH2— (4-Cl—Ph)—C≡C—CH2—
185 (CH3)2N— CH3—CH2—CH2— (4-Cl—Ph)—C≡C—CH2—
186 CH3—CH2—CH2— CH3—CH2—CH2— (4-Cl—Ph)—C≡C—CH2—
187 (CH3)2CH— CH3—CH2—CH2— (4-Cl—Ph)—C≡C—CH2—
188 Cl—CH2—CH2—CH2— CH3—CH2—CH2— (4-Cl—Ph)—C≡C—CH2—
189 CH3—
Figure US06864392-20050308-C00089
 		(4-Cl—Ph)—C≡C—CH2—
190 CH3—CH2—
Figure US06864392-20050308-C00090
 		(4-Cl—Ph)—C≡C—CH2—
191 (CH3)2N—
Figure US06864392-20050308-C00091
 		(4-Cl—Ph)—C≡C—CH2—
192 CH3—CH2—CH2—
Figure US06864392-20050308-C00092
 		(4-Cl—Ph)—C≡C—CH2—
193 (CH3)2CH—
Figure US06864392-20050308-C00093
 		(4-Cl—Ph)—C≡C—CH2—
194 Cl—CH2—CH2—CH2—
Figure US06864392-20050308-C00094
 		(4-Cl—Ph)—C≡C—CH2—
195 CH3— CH2═CH—CH2— (4-Cl—Ph)—C≡C—CH2—
196 CH3—CH2— CH2═CH—CH2— (4-Cl—Ph)—C≡C—CH2—
197 (CH3)2N— CH2═CH—CH2— (4-Cl—Ph)—C≡C—CH2—
198 CH3—CH2—CH2— CH2═CH—CH2— (4-Cl—Ph)—C≡C—CH2—
199 (CH3)2CH— CH2═CH—CH2— (4-Cl—Ph)—C≡C—CH2—
200 Cl—CH2—CH2—CH2— CH2═CH—CH2— (4-Cl—Ph)—C≡C—CH2—
201 CH3— CH≡C—CH2— (4-Cl—Ph)—C≡C—CH2—
202 CH3—CH2— CH≡C—CH2— (4-Cl—Ph)—C≡C—CH2—
203 (CH3)2N— CH≡C—CH2— (4-Cl—Ph)—C≡C—CH2—
204 CH3—CH2—CH2— CH≡C—CH2— (4-Cl—Ph)—C≡C—CH2—
205 (CH3)2CH— CH≡C—CH2— (4-Cl—Ph)—C≡C—CH2—
206 Cl—CH2—CH2—CH2— CH≡C—CH2— (4-Cl—Ph)—C≡C—CH2—
207 CH3— CH3—CH2—CH(CH3)— (4-Cl—Ph)—C≡C—CH2—
208 CH3—CH2— CH3—CH2—CH(CH3)— (4-Cl—Ph)—C≡C—CH2—
209 (CH3)2N— CH3—CH2—CH(CH3)— (4-Cl—Ph)—C≡C—CH2—
210 CH3—CH2—CH2— CH3—CH2—CH(CH3)— (4-Cl—Ph)—C≡C—CH2—
211 (CH3)2CH— CH3—CH2—CH(CH3)— (4-Cl—Ph)—C≡C—CH2—
212 Cl—CH2—CH2—CH2— CH3—CH2—CH(CH3)— (4-Cl—Ph)—C≡C—CH2—
213 CH3— CH3—CH2— (4-Br—Ph)—C≡C—CH2—
214 CH3—CH2— CH3—CH2— (4-Br—Ph)—C≡C—CH2—
215 (CH3)2N— CH3—CH2— (4-Br—Ph)—C≡C—CH2—
216 CH3—CH2—CH2— CH3—CH2— (4-Br—Ph)—C≡C—CH2—
217 (CH3)2CH— CH3—CH2— (4-Br—Ph)—C≡C—CH2—
218 Cl—CH2—CH2—CH2— CH3—CH2— (4-Br—Ph)—C≡C—CH2—
219 CH3— (CH3)2CH— (4-Br—Ph)—C≡C—CH2—
220 CH3—CH2— (CH3)2CH— (4-Br—Ph)—C≡C—CH2—
221 (CH3)2N— (CH3)2CH— (4-Br—Ph)—C≡C—CH2—
222 CH3—CH2—CH2— (CH3)2CH— (4-Br—Ph)—C≡C—CH2—
223 (CH3)2CH— (CH3)2CH— (4-Br—Ph)—C≡C—CH2—
224 Cl—CH2—CH2—CH2— (CH3)2CH— (4-Br—Ph)—C≡C—CH2—
225 CH3— CH3—CH2—CH2— (4-Br—Ph)—C≡C—CH2—
226 CH3—CH2— CH3—CH2—CH2— (4-Br—Ph)—C≡C—CH2—
227 (CH3)2N— CH3—CH2—CH2— (4-Br—Ph)—C≡C—CH2—
228 CH3—CH2—CH2— CH3—CH2—CH2— (4-Br—Ph)—C≡C—CH2—
229 (CH3)2CH— CH3—CH2—CH2— (4-Br—Ph)—C≡C—CH2—
230 Cl—CH2—CH2—CH2— CH3—CH2—CH2— (4-Br—Ph)—C≡C—CH2—
231 CH3—
Figure US06864392-20050308-C00095
 		(4-Br—Ph)—C≡C—CH2—
232 CH3—CH2—
Figure US06864392-20050308-C00096
 		(4-Br—Ph)—C≡C—CH2—
233 (CH3)2N—
Figure US06864392-20050308-C00097
 		(4-Br—Ph)—C≡C—CH2—
234 CH3—CH2—CH2—
Figure US06864392-20050308-C00098
 		(4-Br—Ph)—C≡C—CH2—
235 (CH3)2CH—
Figure US06864392-20050308-C00099
 		(4-Br—Ph)—C≡C—CH2—
236 Cl—CH2—CH2—CH2—
Figure US06864392-20050308-C00100
 		(4-Br—Ph)—C≡C—CH2—
237 CH3— CH2═CH—CH2— (4-Br—Ph)—C≡C—CH2—
238 CH3—CH2— CH2═CH—CH2— (4-Br—Ph)—C≡C—CH2—
239 (CH3)2N— CH2═CH—CH2— (4-Br—Ph)—C≡C—CH2—
240 CH3—CH2—CH2— CH2═CH—CH2— (4-Br—Ph)—C≡C—CH2—
241 (CH3)2CH— CH2═CH—CH2— (4-Br—Ph)—C≡C—CH2—
242 Cl—CH2—CH2—CH2— CH2═CH—CH2— (4-Br—Ph)—C≡C—CH2—
243 CH3— CH≡C—CH2— (4-Br—Ph)—C≡C—CH2—
244 CH3—CH2— CH≡C—CH2— (4-Br—Ph)—C≡C—CH2—
245 (CH3)2N— CH≡C—CH2— (4-Br—Ph)—C≡C—CH2—
246 CH3—CH2—CH2— CH≡C—CH2— (4-Br—Ph)—C≡C—CH2—
247 (CH3)2CH— CH≡C—CH2— (4-Br—Ph)—C≡C—CH2—
248 Cl—CH2—CH2—CH2— CH≡C—CH2— (4-Br—Ph)—C≡C—CH2—
249 CH3— CH3—CH2—CH(CH3)— (4-Br—Ph)—C≡C—CH2—
250 CH3—CH2— CH3—CH2—CH(CH3)— (4-Br—Ph)—C≡C—CH2—
251 (CH3)2N— CH3—CH2—CH(CH3)— (4-Br—Ph)—C≡C—CH2—
252 CH3—CH2—CH2— CH3—CH2—CH(CH3)— (4-Br—Ph)—C≡C—CH2—
253 (CH3)2CH— CH3—CH2—CH(CH3)— (4-Br—Ph)—C≡C—CH2—
254 Cl—CH2—CH2—CH2— CH3—CH2—CH(CH3)— (4-Br—Ph)—C≡C—CH2—
255 CH3— CH3—CH2— H
256 CH3—CH2— CH3—CH2— H
257 (CH3)2N— CH3—CH2— H
258 CH3—CH2—CH2— CH3—CH2— H
259 (CH3)2CH— CH3—CH2— H
260 Cl—CH2—CH2—CH2— CH3—CH2— H
261 CH3— (CH3)2CH— H
262 CH3—CH2— (CH3)2CH— H
263 (CH3)2N— (CH3)2CH— H
264 CH3—CH2—CH2— (CH3)2CH— H
265 (CH3)2CH— (CH3)2CH— H
266 Cl—CH2—CH2—CH2— (CH3)2CH— H
267 CH3— CH3—CH2—CH2— H
268 CH3—CH2— CH3—CH2—CH2— H
269 (CH3)2N— CH3—CH2—CH2— H
270 CH3—CH2—CH2— CH3—CH2—CH2— H
271 (CH3)2CH— CH3—CH2—CH2— H
272 Cl—CH2—CH2—CH2— CH3—CH2—CH2— H
273 CH3—
Figure US06864392-20050308-C00101
 		H
274 CH3—CH2—
Figure US06864392-20050308-C00102
 		H
275 (CH3)2N—
Figure US06864392-20050308-C00103
 		H
276 CH3—CH2—CH2—
Figure US06864392-20050308-C00104
 		H
277 (CH3)2CH—
Figure US06864392-20050308-C00105
 		H
278 Cl—CH2—CH2—CH2—
Figure US06864392-20050308-C00106
 		H
279 CH3— CH2═CH—CH2— H
280 CH3—CH2— CH2═CH—CH2— H
281 (CH3)2N— CH2═CH—CH2— H
282 CH3—CH2—CH2— CH2═CH—CH2— H
283 (CH3)2CH— CH2═CH—CH2— H
284 Cl—CH2—CH2—CH2— CH2═CH—CH2— H
285 CH3— CH≡C—CH2— H
286 CH3—CH2— CH≡C—CH2— H
287 (CH3)2N— CH≡C—CH2— H
288 CH3—CH2—CH2— CH≡C—CH2— H
289 (CH3)2CH— CH≡C—CH2— H
290 Cl—CH2—CH2—CH2— CH≡C—CH2— H
291 CH3— CH3—CH2—CH(CH3)— H
292 CH3—CH2— CH3—CH2—CH(CH3)— H
293 (CH3)2N— CH3—CH2—CH(CH3)— H
294 CH3—CH2—CH2— CH3—CH2—CH(CH3)— H
295 (CH3)2CH— CH3—CH2—CH(CH3)— H
296 Cl—CH2—CH2—CH2— CH3—CH2—CH(CH3)— H
297 CH3— CH3—CH2— Ph—CH2—
298 CH3—CH2— CH3—CH2— Ph—CH2—
299 (CH3)2N— CH3—CH2— Ph—CH2—
300 CH3—CH2—CH2— CH3—CH2— Ph—CH2—
301 (CH3)2CH— CH3—CH2— Ph—CH2—
302 Cl—CH2—CH2—CH2— CH3—CH2— Ph—CH2—
303 CH3— (CH3)2CH— Ph—CH2—
304 CH3—CH2— (CH3)2CH— Ph—CH2—
305 (CH3)2N— (CH3)2CH— Ph—CH2—
306 CH3—CH2—CH2— (CH3)2CH— Ph—CH2—
307 (CH3)2CH— (CH3)2CH— Ph—CH2—
308 Cl—CH2—CH2—CH2— (CH3)2CH— Ph—CH2—
309 CH3— CH3—CH2—CH2— Ph—CH2—
310 CH3—CH2— CH3—CH2—CH2— Ph—CH2—
311 (CH3)2N— CH3—CH2—CH2— Ph—CH2—
312 CH3—CH2—CH2— CH3—CH2—CH2— Ph—CH2—
313 (CH3)2CH— CH3—CH2—CH2— Ph—CH2—
314 Cl—CH2—CH2—CH2— CH3—CH2—CH2— Ph—CH2—
315 CH3—
Figure US06864392-20050308-C00107
 		Ph—CH2—
316 CH3—CH2—
Figure US06864392-20050308-C00108
 		Ph—CH2—
317 (CH3)2N—
Figure US06864392-20050308-C00109
 		Ph—CH2—
318 CH3—CH2—CH2—
Figure US06864392-20050308-C00110
 		Ph—CH2—
319 (CH3)2CH—
Figure US06864392-20050308-C00111
 		Ph—CH2—
320 Cl—CH2—CH2—CH2—
Figure US06864392-20050308-C00112
 		Ph—CH2—
321 CH3— CH2═CH—CH2— Ph—CH2—
322 CH3—CH2— CH2═CH—CH2— Ph—CH2—
323 (CH3)2N— CH2═CH—CH2— Ph—CH2—
324 CH3—CH2—CH2— CH2═CH—CH2— Ph—CH2—
325 (CH3)2CH— CH2═CH—CH2— Ph—CH2—
326 Cl—CH2—CH2—CH2— CH2═CH—CH2— Ph—CH2—
327 CH3— CH≡C—CH2— Ph—CH2—
328 CH3—CH2— CH≡C—CH2— Ph—CH2—
329 (CH3)2N— CH≡C—CH2— Ph—CH2—
330 CH3—CH2—CH2— CH≡C—CH2— Ph—CH2—
331 (CH3)2CH— CH≡C—CH2— Ph—CH2—
332 Cl—CH2—CH2—CH2— CH≡C—CH2— Ph—CH2—
333 CH3— CH3—CH2—CH(CH3)— Ph—CH2—
334 CH3—CH2— CH3—CH2—CH(CH3)— Ph—CH2—
335 (CH3)2N— CH3—CH2—CH(CH3)— Ph—CH2—
336 CH3—CH2—CH2— CH3—CH2—CH(CH3)— Ph—CH2—
337 (CH3)2CH— CH3—CH2—CH(CH3)— Ph—CH2—
338 Cl—CH2—CH2—CH2— CH3—CH2—CH(CH3)— Ph—CH2—
339 CH3— CH3—CH2— (4-Cl—Ph)—CH2—
340 CH3—CH2— CH3—CH2— (4-Cl—Ph)—CH2—
341 (CH3)2N— CH3—CH2— (4-Cl—Ph)—CH2—
342 CH3—CH2—CH2— CH3—CH2— (4-Cl—Ph)—CH2—
343 (CH3)2CH— CH3—CH2— (4-Cl—Ph)—CH2—
344 Cl—CH2—CH2—CH2— CH3—CH2— (4-Cl—Ph)—CH2—
345 CH3— (CH3)2CH— (4-Cl—Ph)—CH2—
346 CH3—CH2— (CH3)2CH— (4-Cl—Ph)—CH2—
347 (CH3)2N— (CH3)2CH— (4-Cl—Ph)—CH2—
348 CH3—CH2—CH2— (CH3)2CH— (4-Cl—Ph)—CH2—
349 (CH3)2CH— (CH3)2CH— (4-Cl—Ph)—CH2—
350 Cl—CH2—CH2—CH2— (CH3)2CH— (4-Cl—Ph)—CH2—
351 CH3— CH3—CH2—CH2— (4-Cl—Ph)—CH2—
352 CH3—CH2— CH3—CH2—CH2— (4-Cl—Ph)—CH2—
353 (CH3)2N— CH3—CH2—CH2— (4-Cl—Ph)—CH2—
354 CH3—CH2—CH2— CH3—CH2—CH2— (4-Cl—Ph)—CH2—
355 (CH3)2CH— CH3—CH2—CH2— (4-Cl—Ph)—CH2—
356 Cl—CH2—CH2—CH2— CH3—CH2—CH2— (4-Cl—Ph)—CH2—
357 CH3—
Figure US06864392-20050308-C00113
 		(4-Cl—Ph)—CH2—
358 CH3—CH2—
Figure US06864392-20050308-C00114
 		(4-Cl—Ph)—CH2—
359 (CH3)2N—
Figure US06864392-20050308-C00115
 		(4-Cl—Ph)—CH2—
360 CH3—CH2—CH2—
Figure US06864392-20050308-C00116
 		(4-Cl—Ph)—CH2—
361 (CH3)2CH—
Figure US06864392-20050308-C00117
 		(4-Cl—Ph)—CH2—
362 Cl—CH2—CH2—CH2—
Figure US06864392-20050308-C00118
 		(4-Cl—Ph)—CH2—
363 CH3— CH2═CH—CH2— (4-Cl—Ph)—CH2—
364 CH3—CH2— CH2═CH—CH2— (4-Cl—Ph)—CH2—
365 (CH3)2N— CH2═CH—CH2— (4-Cl—Ph)—CH2—
366 CH3—CH2—CH2— CH2═CH—CH2— (4-Cl—Ph)—CH2—
367 (CH3)2CH— CH2═CH—CH2— (4-Cl—Ph)—CH2—
368 Cl—CH2—CH2—CH2— CH2═CH—CH2— (4-Cl—Ph)—CH2—
369 CH3— CH≡C—CH2— (4-Cl—Ph)—CH2—
370 CH3—CH2— CH≡C—CH2— (4-Cl—Ph)—CH2—
371 (CH3)2N— CH≡C—CH2— (4-Cl—Ph)—CH2—
372 CH3—CH2—CH2— CH≡C—CH2— (4-Cl—Ph)—CH2—
373 (CH3)2CH— CH≡C—CH2— (4-Cl—Ph)—CH2—
374 Cl—CH2—CH2—CH2— CH≡C—CH2— (4-Cl—Ph)—CH2—
375 CH3— CH3—CH2—CH(CH3)— (4-Cl—Ph)—CH2—
376 CH3—CH2— CH3—CH2—CH(CH3)— (4-Cl—Ph)—CH2—
378 (CH3)2N— CH3—CH2—CH(CH3)— (4-Cl—Ph)—CH2—
379 CH3—CH2—CH2— CH3—CH2—CH(CH3)— (4-Cl—Ph)—CH2—
380 (CH3)2CH— CH3—CH2—CH(CH3)— (4-Cl—Ph)—CH2—
381 Cl—CH2—CH2—CH2— CH3—CH2—CH(CH3)— (4-Cl—Ph)—CH2—
382 CH3— CH3—CH2— (3-Cl—Ph)—CH2—
383 CH3—CH2— CH3—CH2— (3-Cl—Ph)—CH2—
384 (CH3)2N— CH3—CH2— (3-Cl—Ph)—CH2—
385 CH3—CH2—CH2— CH3—CH2— (3-Cl—Ph)—CH2—
386 (CH3)2CH— CH3—CH2— (3-Cl—Ph)—CH2—
387 Cl—CH2—CH2—CH2— CH3—CH2— (3-Cl—Ph)—CH2—
388 CH3— (CH3)2CH— (3-Cl—Ph)—CH2—
389 CH3—CH2— (CH3)2CH— (3-Cl—Ph)—CH2—
390 (CH3)2N— (CH3)2CH— (3-Cl—Ph)—CH2—
391 CH3—CH2—CH2— (CH3)2CH— (3-Cl—Ph)—CH2—
392 (CH3)2CH— (CH3)2CH— (3-Cl—Ph)—CH2—
393 Cl—CH2—CH2—CH2— (CH3)2CH— (3-Cl—Ph)—CH2—
394 CH3— CH3—CH2—CH2— (3-Cl—Ph)—CH2—
395 CH3—CH2— CH3—CH2—CH2— (3-Cl—Ph)—CH2—
396 (CH3)2N— CH3—CH2—CH2— (3-Cl—Ph)—CH2—
397 CH3—CH2—CH2— CH3—CH2—CH2— (3-Cl—Ph)—CH2—
398 (CH3)2CH— CH3—CH2—CH2— (3-Cl—Ph)—CH2—
399 Cl—CH2—CH2—CH2— CH3—CH2—CH2— (3-Cl—Ph)—CH2—
400 CH3—
Figure US06864392-20050308-C00119
 		(3-Cl—Ph)—CH2—
401 CH3—CH2—
Figure US06864392-20050308-C00120
 		(3-Cl—Ph)—CH2—
402 (CH3)2N—
Figure US06864392-20050308-C00121
 		(3-Cl—Ph)—CH2—
403 CH3—CH2—CH2—
Figure US06864392-20050308-C00122
 		(3-Cl—Ph)—CH2—
404 (CH3)2CH—
Figure US06864392-20050308-C00123
 		(3-Cl—Ph)—CH2—
405 Cl—CH2—CH2—CH2—
Figure US06864392-20050308-C00124
 		(3-Cl—Ph)—CH2—
406 CH3— CH2═CH—CH2— (3-Cl—Ph)—CH2—
407 CH3—CH2— CH2═CH—CH2— (3-Cl—Ph)—CH2—
408 (CH3)2N— CH2═CH—CH2— (3-Cl—Ph)—CH2—
409 CH3—CH2—CH2— CH2═CH—CH2— (3-Cl—Ph)—CH2—
410 (CH3)2CH— CH2═CH—CH2— (3-Cl—Ph)—CH2—
411 Cl—CH2—CH2—CH2— CH2═CH—CH2— (3-Cl—Ph)—CH2—
412 CH3— CH≡C—CH2— (3-Cl—Ph)—CH2—
413 CH3—CH2— CH≡C—CH2— (3-Cl—Ph)—CH2—
414 (CH3)2N— CH≡C—CH2— (3-Cl—Ph)—CH2—
415 CH3—CH2—CH2— CH≡C—CH2— (3-Cl—Ph)—CH2—
416 (CH3)2CH— CH≡C—CH2— (3-Cl—Ph)—CH2—
417 Cl—CH2—CH2—CH2— CH≡C—CH2— (3-Cl—Ph)—CH2—
418 CH3— CH3—CH2—CH(CH3)— (3-Cl—Ph)—CH2—
419 CH3—CH2— CH3—CH2—CH(CH3)— (3-Cl—Ph)—CH2—
420 (CH3)2N— CH3—CH2—CH(CH3)— (3-Cl—Ph)—CH2—
421 CH3—CH2—CH2— CH3—CH2—CH(CH3)— CH(CH3)—(3-Cl—Ph)—CH2—
422 (CH3)2CH— CH3—CH2—CH(CH3)— (3-Cl—Ph)—CH2—
423 Cl—CH2—CH2—CH2— CH3—CH2—CH(CH3)— (3-Cl—Ph)—CH2—
424 CH3— CH3—CH2— (3-CF3—Ph)—CH2—
425 CH3—CH2— CH3—CH2— (3-CF3—Ph)—CH2—
426 (CH3)2N— CH3—CH2— (3-CF3—Ph)—CH2—
427 CH3—CH2—CH2— CH3—CH2— (3-CF3—Ph)—CH2—
428 (CH3)2CH— CH3—CH2— (3-CF3—Ph)—CH2—
429 Cl—CH2—CH2—CH2— CH3—CH2— (3-CF3—Ph)—CH2—
430 CH3— (CH3)2CH— (3-CF3—Ph)—CH2—
431 CH3—CH2— (CH3)2CH— (3-CF3—Ph)—CH2—
432 (CH3)2N— (CH3)2CH— (3-CF3—Ph)—CH2—
433 CH3—CH2—CH2— (CH3)2CH— (3-CF3—Ph)—CH2—
434 (CH3)2CH— (CH3)2CH— (3-CF3—Ph)—CH2—
435 Cl—CH2—CH2—CH2— (CH3)2CH— (3-CF3—Ph)-CH2—
436 CH3— CH3—CH2—CH2— (3-CF3—Ph)—CH2—
437 CH3—CH2— CH3—CH2—CH2— (3-CF3—Ph)—CH2—
438 (CH3)2N— CH3—CH2—CH2— (3-CF3—Ph)—CH2—
439 CH3—CH2—CH2— CH3—CH2—CH2— (3-CF3—Ph)—CH2—
440 (CH3)2CH— CH3—CH2—CH2— (3-CF3—Ph)—CH2—
441 Cl—CH2—CH2—CH2— CH3—CH2—CH2— (3-CF3—Ph)—CH2—
442 CH3—
Figure US06864392-20050308-C00125
 		(3-CF3—Ph)—CH2—
443 CH3—CH2—
Figure US06864392-20050308-C00126
 		(3-CF3—Ph)—CH2—
444 (CH3)2N—
Figure US06864392-20050308-C00127
 		(3-CF3—Ph)—CH2—
445 CH3—CH2—CH2—
Figure US06864392-20050308-C00128
 		(3-CF3—Ph)—CH2—
446 (CH3)2CH—
Figure US06864392-20050308-C00129
 		(3-CF3—Ph)—CH2—
447 Cl—CH2—CH2—CH2—
Figure US06864392-20050308-C00130
 		(3-CF3—Ph)—CH2—
448 CH3— CH2═CH—CH2— (3-CF3—Ph)—CH2—
449 CH3—CH2— CH2═CH—CH2— (3-CF3—Ph)—CH2—
450 (CH3)2N— CH2═CH—CH2— (3-CF3—Ph)—CH2—
451 CH3—CH2—CH2— CH2═CH—CH2— (3-CF3—Ph)—CH2—
452 (CH3)2CH— CH2═CH—CH2— (3-CF3—Ph)—CH2—
453 Cl—CH2—CH2—CH2— CH2═CH—CH2— (3-CF3—Ph)—CH2—
454 CH3— CH≡C—CH2— (3-CF3—Ph)—CH2—
455 CH3—CH2— CH≡C—CH2— (3-CF3—Ph)—CH2—
456 (CH3)2N— CH≡C—CH2— (3-CF3—Ph)—CH2—
457 CH3—CH2—CH2— CH≡C—CH2— (3-CF3—Ph)—CH2—
458 (CH3)2CH— CH≡C—CH2— (3-CF3—Ph)—CH2—
459 Cl—CH2—CH2—CH2— CH═C—CH2— (3-CF3—Ph)—CH2—
460 CH3— CH3—CH2—CH(CH3)— (3-CF3—Ph)—CH2—
461 CH3—CH2— CH3—CH2—CH(CH3)— (3-CF3—Ph)—CH2—
462 (CH3)2N— CH3—CH2—CH(CH3)— (3-CF3—Ph)—CH2—
463 CH3—CH2—CH2— CH3—CH2—CH(CH3)— (3-CF3—Ph)—CH2—
464 (CH3)2CH— CH3—CH2—CH(CH3)— (3-CF3—Ph)—CH2—
465 Cl—CH2—CH2—CH2— CH3—CH2—CH(CH3)— (3-CF3—Ph)—CH2—
TABLE 7
Compounds represented by the Formula I.7 where the combination of the groups
R1, and R3 corresponds to each row in table B.
I.7
Figure US06864392-20050308-C00131
TABLE 8
Compounds represented by the Formula I.8 where the combination of
the groups R1, and R3 corresponds to each row in table B.
Figure US06864392-20050308-C00132
 		I.8
TABLE 9
Compounds represented by the Formula I.9 where the combination of
the groups R1, and R3 corresponds to each row in table B.
Figure US06864392-20050308-C00133
 		I.9
TABLE 10
Compounds represented by the Formula I.10 where the combination of
the groups R1, and R3 corresponds to each row in table B.
Figure US06864392-20050308-C00134
 		I.10
TABLE 11
Compounds represented by the Formula I.11 where the combination of
the groups R1, and R3 corresponds to each row in table B.
Figure US06864392-20050308-C00135
 		I.11
TABLE 12
Compounds represented by the Formula I.12 where the
combination of the groups R1, and R3
corresponds to each row in table B.
1.12
Figure US06864392-20050308-C00136
TABLE B
No. R1 R3
001 (CH3—CH2)2N— CH3—CH2—
002 CH3—CH2—(CH3)N— CH3—CH2—
003
Figure US06864392-20050308-C00137
 		CH3—CH2—
004 CH3—(CH2)2—CH2— CH3—CH2—
005 (CH3)2CH—CH2— CH3—CH2—
006 CH3—CH2—(CH3)CH— CH3—CH2—
007 (CH3)3C— CH3—CH2—
008 CH2═CH— CH3—CH2—
009
Figure US06864392-20050308-C00138
 		CH3—CH2—
010 (CH3—CH2)2N— (CH3)2CH—
011 CH3—CH2—(CH3)N— (CH3)2CH—
012
Figure US06864392-20050308-C00139
 		(CH3)2CH—
013 CH3—(CH2)2—CH2— (CH3)2CH—
014 (CH3)2CH—CH2— (CH3)2CH—
015 CH3—CH2—(CH3)CH— (CH3)2CH—
016 (CH3)3C— (CH3)2CH—
017 CH2═CH— (CH3)2CH—
018
Figure US06864392-20050308-C00140
 		(CH3)2CH—
019 (CH3—CH2)2N— CH3—CH2—CH2
020 CH3—CH2—(CH3)N— CH3—CH2—CH2
021
Figure US06864392-20050308-C00141
 		CH3—CH2—CH2
022 CH3—(CH2)2—CH2— CH3—CH2—CH2
023 (CH3)2CH—CH2— CH3—CH2—CH2
024 CH3—CH2—(CH3)CH— CH3—CH2—CH2
025 (CH3)3C— CH3—CH2—CH2
026 CH2═CH— CH3—CH2—CH2
027
Figure US06864392-20050308-C00142
 		CH3—CH2—CH2
028 (CH3—CH2)2N— CH3—CH2—(CH3)CH—
029 CH3—CH2—(CH3)N— CH3—CH2—(CH3)CH—
030
Figure US06864392-20050308-C00143
 		CH3—CH2—(CH3)CH—
031 CH3—(CH2)2—CH2— CH3—CH2—(CH3)CH—
032 (CH3)2CH—CH2— CH3—CH2—(CH3)CH—
033 CH3—CH2—(CH3)CH— CH3—CH2—(CH3)CH—
034 (CH3)3C— CH3—CH2—(CH3)CH—
035 CH2═CH— CH3—CH2—(CH3)CH—
036
Figure US06864392-20050308-C00144
 		CH3—CH2—(CH3)CH—
037 (CH3—CH2)2N—
Figure US06864392-20050308-C00145
038 CH3—CH2—(CH3)N—
Figure US06864392-20050308-C00146
039
Figure US06864392-20050308-C00147
Figure US06864392-20050308-C00148
040 CH3(CH2)2—CH2—
Figure US06864392-20050308-C00149
041 (CH3)2CH—CH2—
Figure US06864392-20050308-C00150
042 CH3—CH2—(CH3)CH—
Figure US06864392-20050308-C00151
043 (CH3)3C—
Figure US06864392-20050308-C00152
044 CH2═CH—
Figure US06864392-20050308-C00153
045
Figure US06864392-20050308-C00154
Figure US06864392-20050308-C00155
046 CH3— HO—CH2—
047 CH3—CH2— HO—CH2—
048 (CH3)2N— HO—CH2—
049 CH3—CH2—CH2— HO—CH2—
050 (CH3)2CH— HO—CH2—
051 CH3—CH2—(CH3)CH— HO—CH2—
052 CH3— HO—(CH3)CH—
053 CH3—CH2— HO—(CH3)CH—
054 (CH3)2N— HO—(CH3)CH—
055 CH3—CH2—CH2— HO—(CH3)CH—
056 (CH3)2CH— HO—(CH3)CH—
057 CH3—CH2—(CH3)CH— HO—(CH3)CH—
058 CH3— (CH3)3C—O—(CH3)CH—
059 CH3—CH2— (CH3)3C—O—(CH3)CH—
060 (CH3)2N— (CH3)3C—O—(CH3)CH—
061 CH3—CH2—CH2— (CH3)3C—O—(CH3)CH—
062 (CH3)2CH— (CH3)3C—O—(CH3)CH—
063 CH3—CH2—(CH3)CH— (CH3)3C—O—(CH3)CH—
064 CH3— CH3—S—CH2—CH2—
065 CH3—CH2— CH3—S—CH2—CH2—
066 (CH3)2N— CH3—S—CH2—CH2—
067 CH3—CH2—CH2— CH3—S—CH2—CH2—
068 (CH3)2CH— CH3—S—CH2—CH2—
069 CH3—CH2—(CH3)CH— CH3—S—CH2—CH2—
070 CH3— HS—CH2—CH2—
071 CH3—CH2— HS—CH2—CH2—
072 (CH3)2N— HS—CH2—CH2—
073 CH3—CH2—CH2— HS—CH2—CH2—
074 (CH3)2CH— HS—CH2—CH2—
075 CH3—CH2—(CH3)CH— HS—CH2—CH2—
076 CH3— (CH3)3C—
077 CH3—CH2— (CH3)3C—
078 (CH3)2N— (CH3)3C—
079 CH3—CH2—CH2— (CH3)3C—
080 (CH3)2CH— (CH3)3C—
081 CH3—CH2—(CH3)CH— (CH3)3C—
TABLE 13
Compounds represented by the Formula I.13 where the combination of
the group R8 corresponds to each row in table C.
Figure US06864392-20050308-C00156
 		I.13
TABLE 14
Compounds represented by the Formula I.14 where the combination of
the group R8 corresponds to each row in table C.
Figure US06864392-20050308-C00157
 		I.14
TABLE 15
Compounds represented by the Formula 1.15 where the combination
of the group R8 corresponds to each row in table C.
1.15
Figure US06864392-20050308-C00158
TABLE C
No. R8
001 CH3—CH2—C(CH3)H—C≡C—CH2—
002 (CH3)3C—C≡C—CH2—
003 (CH3)2CH—CH2—C≡C—CH2—
004 CH3—(CH2)4—C≡C—CH2—
005
Figure US06864392-20050308-C00159
006
Figure US06864392-20050308-C00160
007 (4-CH3—Ph)—C≡C—CH2—
008 (2-Cl—Ph)—C≡C—CH2—
009 (3-Cl—Ph)—C≡C—CH2—
010 (3-Br—Ph)—C≡C—CH2—
011 (3-F—Ph)—C≡C—CH2—
012 (3-CH3—Ph)—C≡C—CH2—
013 (2,4-di-Cl—Ph)—C≡C—CH2—
014 (3,4-di-Cl—Ph)—C≡C—CH2—
015 (3,4-di-F—Ph)—C≡C—CH2—
016 (3-CH3-4-Cl—Ph)—C≡C—CH2—
017 (3-CH3-4-Br—Ph)—C≡C—CH2—
018 (3-CF3—Ph)—C≡C—CH2—
019 (4-CF3O—Ph)—C≡C—CH2—
020 (4-Et—Ph)—C≡C—CH2—
021 [4-(CH3)3C—Ph]—C≡C—CH2—
022 (4-CH2═CH—Ph)—C≡C—CH2—
023 (4-CH≡C—Ph)—C≡C—CH2—
024 (4-CH3—CO—Ph)—C≡C—CH2—
025 (4-CH3OOC—Ph)—C≡C—CH2—
026 (4-CH3O—Ph)—C≡C—CH2—
027
Figure US06864392-20050308-C00161
028
Figure US06864392-20050308-C00162
029
Figure US06864392-20050308-C00163
030
Figure US06864392-20050308-C00164
031 Ph—(CH3)CH—
032 Ph—(CH3)2C—
033 (3-F—Ph)—CH2—
034 (4-Br—Ph)—CH2—
035 (4-J—Ph)—CH2—
036 (4-CH3—Ph)—CH2—
037 (4-CH3O—Ph)—CH2—
038 (4-CF3O—Ph)—CH2—
039 (4-F—Ph)—CH2—
040 (2,4-di-F—Ph)—CH2—
041 (3,4-di-F—Ph)—CH2—
042 (3,4-di-Br—Ph)—CH2—
043 (3,4-di-Cl—Ph)—CH2—
044 (3-Cl-4-CH3-Ph)—CH 2—
045 (3-CH3-4-Cl—Ph)—CH2—
046 (2,4,5-tri-Cl—Ph)—CH2—
047
Figure US06864392-20050308-C00165
048
Figure US06864392-20050308-C00166
049
Figure US06864392-20050308-C00167
050
Figure US06864392-20050308-C00168
051
Figure US06864392-20050308-C00169
052
Figure US06864392-20050308-C00170
053
Figure US06864392-20050308-C00171
054
Figure US06864392-20050308-C00172
055
Figure US06864392-20050308-C00173
056
Figure US06864392-20050308-C00174
057 Ph—CH═CH—CH2—
058 (4-Cl—Ph)—CH═CH—CH2—
059 (4-F—Ph)—CH═CH—CH2—
060 (4-Br—Ph)—CH═CH—CH2—
061 (3-CF3—Ph)—CH═CH2—
062 Ph—CH2—CH2—
063 Ph—(CH2)2—CH2—
064 (4-Cl—Ph)—(CH2)2—CH2—
065 (4-Br—Ph)—(CH2)2—CH2—
066 Ph—O—CH2—CH2—
067 (4-Cl—Ph)—O—CH2—CH2—
068 (4-F—Ph)—O—CH2—CH2—
069 (4-Br—Ph)—O—CH2—CH2—
070 (3-F—Ph)—O—CH2—CH2—
071 (3,4-di-Cl—Ph)—O—CH2—CH2—
072 (4-Cl—Ph)—O—(CH3)CH—CH2—
073 (3,4-di-Cl—Ph)—O—(CH3)CH—CH2—
074 Ph—N(CH3)—CH2—CH2—
075 Ph—N(CH2—CH3)—CH2—CH2—
076 Ph—S—CH2—CH2—
077 (4-Cl—Ph)—S—CH2—CH2—
Formulations may be prepared analogously to those described in, for example, WO 95/30651.
BIOLOGICAL EXAMPLES D-1: Action Against Plasmopara viticola (Downy Mildew) on Vines
5 week old grape seedlings cv. Gutedel are treated with the formulated test compound in a spray chamber. One day after application grape plants are inoculated by spraying a sporangia suspension (4×104 sporangia/ml) on the lower leaf side of the test plants. After an incubation period of 6 days at +21° C. and 95% r. h. in a greenhouse the disease incidence is assessed.
Compounds of Tables 1 to 15 exhibit a good fungicidal action against Plasmopara viticola on vines. Compounds A1.1, A1.2, A1.3, A1.4, A1.5 and A1.6 at 200 ppm inhibit fungal infestation in this test to a least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.
D-2: Action Against Phytophthora (Late Blight) on Tomato Plants
3 week old tomato plants cv. Roter Gnom are treated with the formulated test compound in a spray chamber. Two day after application the plants are inoculated by spraying a sporangia suspension (2×104 sporangia/mI) on the test plants. After an incubation period of 4 days at +18° C. and 95% r. h. in a growth chamber the disease incidence is assessed. Compounds of Tables 1 to 15 exhibit a long-lasting effect against fungus infestation. Compounds A1.1, A1.2, A1.3, A1.4, A1.5 and A1.6 at 200 ppm inhibit fungal infestation in this test to a least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.
D-3: Action Against Phytophthora (Late Blight) on Potato Plants
5 week old potato plants cv. Bintje are treated with the formulated test compound in a spray chamber. Two day after application the plants are inoculated by spraying a sporangia suspension (14×104 sporangia/ml) on the test plants. After an incubation period of 4 days at +18° C. and 95% r. h. in a growth chamber the disease incidence is assessed. Fungal infestation is effectively controlled with compounds of Tables 1 to 15. Compounds A1.1, A1.2, A1.3, A1.4, A1.5 and A1.6 at 200 ppm inhibit fungal infestation in this test to a least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.

Claims (15)

1. α-sulfin- and α-sulfonamino acid amides of formula I
Figure US06864392-20050308-C00175
including the optical isomers thereof and mixtures of such isomers,
wherein
n is a number zero or one;
R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfonyl, C3-C8cycloalkyl, cyano, C1-C6alkoxycarbonyl, C3-C6alkenyloxycarbonyl or C3-C8alkynyloxycarbonyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12halogenalkyl; or a group NR9R10 wherein R9 and R10 are each independently of the other C1-C6alkyl, or together are tetra- or penta-methylene;
R2 and R3 are each independently hydrogen; C1-C8alkyl; C1-C8alkyl substituted with hydroxy, mercapto, C1-C4alkoxy or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl; C3-C3cycloalkyl-C1-C4alkyl; or the two groups R2 and R3 together with the carbon atom to which they are bonded form a three- to eight-membered hydrocarbon ring;
R4, R5, R6 and R7 are each independently hydrogen or C1-C4alkyl;
Figure US06864392-20050308-C00176
R11, R12, R14, R15 and R17 are each independently hydrogen or C1-C4alkyl,
R13 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl,
R16 is optionally substituted aryl or optionally substituted heteroaryl; and
Z is oxygen, sulfur —CR18R19— or —NR20—, wherein R18, R19 and R20 independently of each other are hydrogen or C1-C4alkyl.
2. A compound according to claim 1 wherein n is one.
3. A compound of formula I according to claim 1 wherein
R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, or C1-C4alkylsulfonyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12halogenalkyl; or a group NR9R10 wherein R9 and R10 are each independently of the other hydrogen or C1-C6alkyl, or together are tetra- or penta-methylene.
4. A compound of formula I according to claim 1 wherein
R2 is hydrogen and R3 is C1-C8alkyl, C1-C8alkyl, optionally substituted by hydroxy, C1-C4alkoxy, mercapto or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl or C3-C8cycloalkyl-C1-C4alkyl.
5. A compound of formula I according to claim 1 wherein R4 is hydrogen, methyl or ethyl.
6. A compound of formula I according to claim 1 wherein
R5, R6 and R7 are each independently hydrogen or methyl.
7. A compound of formula I according to claim 1 wherein
R11, R12, R14, R15 and R17 are each independently hydrogen or methyl.
8. A compound of formula I according to claim 1 wherein
R13 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur.
9. A compound of formula I according to claim 1 wherein
R16 is optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur.
10. A compound of formula I according to claim 1 wherein Z is oxygen, sulfur or —CH2—.
11. A compound of formula I according to claim 1 wherein
n is one;
R1 is C1-C4alkyl, vinyl; C1-C4halogenalkyl; or dimethylamino;
R2 is hydrogen and R3 is isopropyl;
R4, R5, R6, R7, R11, R12, R14, R15 and R17 are each hydrogen;
R13 is C4-C8alkyl; C1-C6halogenalkyl; C3-C8cycloalkyl; phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalkyl, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl;
R16 is phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalky, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; and
Z is oxygen.
12. A process for the preparation of a compound of formula I according to claim 1, which comprises reacting
a) an amino acid of formula II or a carboxy-activated derivative thereof
Figure US06864392-20050308-C00177
 wherein R1, n, R2 and R3 are as defined for formula I is reacted with an amine of formula III
Figure US06864392-20050308-C00178
 wherein R4, R5, R6, R7 and R8 are as defined for formula I optionally in the presence of a base and optionally in the presence of a diluting agent, or
b) an amino acid derivative of formula VI
Figure US06864392-20050308-C00179
 wherein R2, R3, R4, R5, R6, R7 and R8 are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V
Figure US06864392-20050308-C00180
 wherein R1 and n are as defined for formula I and X is halide, preferentially chlorine or bromine, or
c) a phenol of formula VII
Figure US06864392-20050308-C00181
 wherein R1, n, R2, R3, R4, R5, R6 and R7 are as defined for formula I with a compound of formula VIII
Figure US06864392-20050308-C00182
 wherein R8 is as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate.
13. A process for the preparation of a compound of formula Ia
Figure US06864392-20050308-C00183
wherein R1, n, R2, R3, R4, R5, R6, R7, R11, R12 and R13 are defined in claim 1 for formula I which comprises reacting a compound of formula IX
Figure US06864392-20050308-C00184
wherein R1, n, R2, R3, R4, R5, R6, R7, R11, R12 and R13 are defined for formula I with hydrogen.
14. A composition for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula I according to claim 1 as active ingredient together with a suitable carrier.
15. A method of controlling and preventing an infestation of crop plants by phytopathogenic microorganisms, preferably fungal organisms, which comprises the application of a compound of formula I according to claim 1 as active ingredient to the plant, to parts of plants or to the locus thereof.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050192359A1 (en) * 2002-03-15 2005-09-01 Sumitomo Chemical Company, Limited N-biphenylamides and fungicidal compositions containing the same

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992000958A1 (en) 1990-07-12 1992-01-23 James Black Foundation Limited Derivatives of aspartic acid and glutamic acid having anti-cholecystokinin activity
WO1995030651A1 (en) 1994-05-04 1995-11-16 Ciba-Geigy Ag N-sulphonyl and n-sulphinyl amino acid amides as microbiocides
US6194463B1 (en) * 1997-02-25 2001-02-27 Novartis Crop Protection, Inc. N-sulphonyl and N-sulphinyl amino acid amides as microbicides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992000958A1 (en) 1990-07-12 1992-01-23 James Black Foundation Limited Derivatives of aspartic acid and glutamic acid having anti-cholecystokinin activity
WO1995030651A1 (en) 1994-05-04 1995-11-16 Ciba-Geigy Ag N-sulphonyl and n-sulphinyl amino acid amides as microbiocides
US5585519A (en) * 1994-05-04 1996-12-17 Ciba-Geigy Corporation Microbicides
US6194463B1 (en) * 1997-02-25 2001-02-27 Novartis Crop Protection, Inc. N-sulphonyl and N-sulphinyl amino acid amides as microbicides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050192359A1 (en) * 2002-03-15 2005-09-01 Sumitomo Chemical Company, Limited N-biphenylamides and fungicidal compositions containing the same

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